research communications
Crystal structures of five 6-mercaptopurine derivatives
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 da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007, Porto, Portugal, cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and dCIQ/Departamento de Quιmica e Bioquιmica, Faculdade de Ciências, Universidade do Porto, 4169-007 Porto, Portugal
*Correspondence e-mail: jnlow111@gmail.com
The crystal structures of five 6-mercaptopurine derivatives, viz. 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(3-methoxyphenyl)ethan-1-one (1), C16H14N4O3S, 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-methoxyphenyl)ethan-1-one (2), C16H14N4O3S, 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-chlorophenyl)ethan-1-one (3), C15H11ClN4O2S, 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-bromophenyl)ethan-1-one (4), C15H11BrN4O2S, and 1-(3-methoxyphenyl)-2-[(9H-purin-6-yl)sulfanyl]ethan-1-one (5), C14H12N4O2S. Compounds (2), (3) and (4) are isomorphous and accordingly their molecular and supramolecular structures are similar. An analysis of the dihedral angles between the purine and exocyclic phenyl rings show that the molecules of (1) and (5) are essentially planar but that in the case of the three isomorphous compounds (2), (3) and (4), these rings are twisted by a dihedral angle of approximately 38°. With the exception of (1) all molecules are linked by weak C—H⋯O hydrogen bonds in their crystals. There is π–π stacking in all compounds. A Cambridge Structural Database search revealed the existence of 11 deposited compounds containing the 1-phenyl-2-sulfanylethanone scaffold; of these, only eight have a cyclic ring as substituent, the majority of these being heterocycles.
Keywords: crystal structure; mercaptopurines; supramolecular structure.
1. Chemical context
Purines, purine ). These types of heterocycles take part of the core structure of guanine and adenine in (DNA and RNA) being involved in diverse in vivo catabolic and anabolic metabolic pathways.
and their analogs, are nitrogen-containing heterocycles ubiquitous in nature and present in biological systems like man, plants and marine organisms (Legraverend, 20086-Mercaptopurine is a water insoluble purine analogue, which attracted attention due to its antitumor and immunosuppressive properties. The drug is used, among others, in the treatment of rheumathologic disorders, cancer and prevention of rejection of organ transplantation. The main problem associated with the pharmacological treatment with 6-mercaptopurine is the low bioavailability of the oral absorption and the short half-life in plasma. Strategies that have been adopted to circumvent those problems include the administration of 6-mercaptopurine analogues that act as prodrugs or by the chemical protection of the thiol group.
Chemically, the 6-mercaptopurine scaffold can also be modulated by an appropriate selection of the substituents that can be located at C-2, N-1, C-6, N-3, C-8, N-7 and N-9 positions, generating a variety of derivatives with potential biological applications (Legraverend & Grierson, 2006; Tunçbilek, et al., 2009).
Within this framework, the goal of this project has been focused on the functionalization of 6-mercapto purine at positions 6 and 9. Here we describe the syntheses and characterization of five 6-mercaptopurine derivatives: 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(3-methoxyphenyl)ethan-1-one (1), 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-methoxyphenyl)ethan-1-one (2), 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-chlorophenyl)ethan-1-one (3), 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-bromophenyl)ethan-1-one (4) and 1-(3-methoxyphenyl)-2-[(9H-purin-6-yl)sulfanyl]ethan-1-one (5).
2. Structural commentary
Compounds (1)–(5) are shown in the scheme and their ellipsoid plots are shown in Figs. 1–5. Compounds (1) and (5) have similar a and c axes and (2), (3) and (4) are isostructural and isomorphous.
These compounds can be envisaged as two building blocks, a substituted phenylethanone grouping and a substituted 6-mercaptopurine moiety, bonded together by the mercapto ethanone residue. Since both purine and phenyl rings are essentially planar, the structural conformations of those compounds are conditioned by the –SCH2CO spacer (Fig. 6) which permits rotations around the following bonds: Pu—S6, S6—C61, C61—C62 and C62—Ph bonds. The sp3 character of the central carbon atom may also direct the relative positions of the acetophenone residue out of the main plane constituted by the mercaptopurine, which is not the case of the present compounds. Selected geometric parameters for compounds (1)–(5) are given in Tables 1–5, respectively.
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The Pu—S6 bond tends to be coplanar with the purine residue. In fact, the 6-mercaptopurine itself may appear in the thione form, e.g. 3,7-dihydropurine-6-thione, as a consequence of the high degree of electron delocalization within the 6-mercaptopurine environment. The tendency for the Pu—S6 bond to assume partial double-bond character is also seen in the present compounds, for which the corresponding Pu—S6 bond lengths lie between 1.741 (3) Å for (2) and 1.755 (3) Å for (4). In contrast, the S6—C61 bond lengths are longer, with values lying between 1.8017 (18) Å in (1) and 1.812 (3) Å in (4). This bond can also be bent with respect to the main mercaptopurine plane. The degree of bending may be evaluated by the distance of the C62 carbon atom from the mean plane consisting of the mercaptopyrimidine atoms. Those values [0.307 (3), 0.272 (4), 0.333 (2), 0.332 (4) and 0.164 (2) for (1)–(5), respectively] show that the degree of bending is higher in (1)–(4) than in (5). As regards the ethanone group, the C61—C62 bond lengths lie in the range 1.510 (4) Å (2) to 1.528 (4) Å, (4) and are normal for a Csp3—Csp3 bond while the C62—Ph bond lengths are shorter and lie in the range 1.474 (3) Å (2) to 1.496 (4) (4), suggesting that the electron density is delocalized from the phenyl ring.
The dihedral angles between the mean planes of the of the purine and phenyl ring, θ1, those between the mean plane of the purine ring and the plane defined by the S6—C61—C62—O6 atoms, θ2, and those between the mean planes of the phenyl ring and the plane defined by the S6—C61—C62—O6 atoms, θ3 are given in Table 6. These values show that the molecules of (1) and (5) are essentially planar. However, in the case of the three isomorphous compounds (2), (3) and (4), the purine and exocyclic phenyl rings are both twisted in the opposite direction from the plane of the bridging unit, resulting in a dihedral angle of approximately 38°. This is due to the rotations and bending around the bonds connecting the bridging unit to the purine and exocyclic phenyl rings as discussed above. The dihedral angles θ2 are higher than θ3; the former are mainly due to the rotations around the S6—C61 bond while the latter are mainly the result of the bending of the C62—Ph bond.
3. Supramolecular features
There are no weak C—H⋯O or C—H⋯N contacts in (1). Hydrogen bonds for (2)–(5) are listed in Tables 7–10, respectively. Since (2), (3) and (4) are isomorphous, their supramolecular structures follow similar patterns. Accordingly, hydrogen-bonding diagrams are given for (2) only. Atom C8 acts as a donor to O9 (−x − 1, −y + 1, −z + 1), via H8 forming an R22(10) centrosymmetric dimer across the inversion centre at (−1/2, 1/2, 1/2), Fig. 7. Atom C61 makes a hydrogen bond with O6 (−x + 1, y + , −z + ), via H61A, forming a C4 chain, which runs parallel to the b axis, Fig. 8, generated by the twofold screw axis at (1/2, y, 1/4). In (2), there is a short contact between C6 and the 4-methoxy atom O64 (−x + 2, y + , −z + ), forming a C12 chain, Fig. 9, which runs parallel to the b axis and is generated by the twofold screw axis at (1, y, ). In (5), the N9—H9⋯N9 (x − , −y + , z − ) hydrogen bond, Fig. 10, links the molecules into a C4 chain which runs parallel to [01] and which is generated by the n-glide plane at (0, , 0).
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Since those compounds have three rings, the imidazole ring (with centroid Cg1), the pyrimidine ring (with centroid Cg2) and the benzyl ring (with centroid Cg3), it would be expected that π–π contacts were part of the supramolecular structure. Table 11 lists the possible π–π contacts for (1)–(5). As may be seen in the Table, the pyrimidine ring establishes π–π contacts with the benzyl ring for all compounds. In (1), two molecules centrosymmetrically related across the inversion centre at (0, ½, ½) are involved in π–π stacking in which the purine ring stacks above the exocyclic phenyl ring. In (2), (3) and (4), the π–π stacking is between imidazole rings while in (1) and (5), the contact is between an imidazole ring and a benzyl ring. In particular, in (1) and (5) two molecules centrosymmetrically related across the centre of symmetry at (0, ½, ½) are involved in π–π stacking in which the purine rings stack above the exocyclic phenyl ring, Table 11.
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4. Database survey
A search made in the Cambridge Structural Database (Groom & Allen, 2014) revealed the existence of 11 deposited compounds containing the 2-thio-1-phenylethanone scaffold (see supplementary Figure). Of those, only eight have a cyclic ring as substituent, the majority of these being heterocycles: MUCCUJ: 2-(1,3-benzoxazol-2-ylsulfanyl)-1-phenylethanone (Loghmani-Khouzani et al., 2009a); NENFAO: 3-(benzoylmethylthio)-1,5-diphenyl-1H-1,2,4-triazole (Liu et al., 2006); PUFGED: 2-(1,3-benzothiazol-2-ylsulfanyl)-1-phenylethanone (Loghmani-Khouzani et al., 2009b); IKAXOI: 6-cyclohexylmethyl-5-ethyl-2-[(2-oxo-2-phenylethyl)sulfanyl]pyrimidin-4(3H)-οne (Yan et al., 2011); SILGAW: 2-(benzoylmethylsulfanyl)-6-benzyl-5-isopropylpyrimidin-4(3H)-one (Rao et al., 2007); ETEWOP: 2-(benzoylmethylsulphanyl)-6-methoxy-1H-benzamide (Lynch & McLenaghan, 2004); XEBWEI: 2-(1,3-benzimidazolol-2-ylsulfanyl)phenylethanone (Abdel-Aziz et al., 2012); UGITUA: 2-[(4-methoxybenzyl)sulfanyl]-1-phenylethanone (Heravi et al., 2009).
The R—S bond distances for these compounds are similar to those of the studied compounds and they assume a partial double-bond character with the exception of UGITUA where the S atom is bonded to a phenyl ring, suggesting a tendency for delocalization of the electron density through the sulfur atom when the ring has heteroatoms. The S—CH2 bond distances vary between 1.80 and 1.81 Å with exception of SILGAW (1.79 Å) and ETEWOP (1.82 Å). The supplementary figure also gives information about the distances of the –CH2– carbon atom to the best plane made up of the atoms of the heterocycles (CH2– distance). These values were computed in order to evaluate the degree of bending of the S—CH2 bond with respect to the main plane of the substituted rings. There are two main groups of compounds, one in which the distance is shorter than 0.3 Å and the other, which contains the CNH fragment in the heterocyclic ring, in which this distance is greater than 1.2 Å. As noted above, the sp3 character of the β-carbon atom of the ethanone fragment may also direct the relative positions of the acetophenone residue out of the main plane constituted by the substituted heteroaromatic ring. This is the case for SILGAW and IKAXOI. Thus, despite the small sample size, there is a wide range of adopted conformations.
5. Synthesis and crystallization
The 6-mercaptopurine derivatives (1)–(5) were obtained in moderate yields by a two-step synthetic strategy. Firstly, 6-mercaptopurine was alkylated using diverse monobromide acetophenone derivatives in DMF/potassium carbonate medium at room temperature (Lambertucci, et al. 2009). After thiol alkylation, the purine nucleus was acylated in position 9 with acetic anhydride in triethylamine and anhydrous DMF for (1)–(4) under an argon atmosphere at room temperature (Masai, et al. 2002). All compounds were recrystallized from dichloromethane solution: 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(3-methoxyphenyl)ethan-1-one (1): overall yield: 48%; m.p. 432–435 K; 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-methoxyphenyl)ethan-1-one (2): overall yield: 17%; m.p. 460–463 K; 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-chlorophenyl)ethan-1-one (3): overall yield: 26%; m.p. 453–457 K; 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-bromophenyl)ethan-1-one (4): overall yield: 10%; m.p. 449–451 K; 1-(3-methoxyphenyl)-2-[(9H-purin-6-yl)sulfanyl]ethan-1-one (5): overall yield: 55%; m.p. 461–464 K.
6. Refinement
Crystal data, data collection and structure . H atoms were treated as riding atoms with C—H(aromatic), 0.95 Å, with Uiso = 1.2Ueq(C), C—H2(methylene), 0.99 Å, with Uiso = 1.2Ueq(C),C—H(methyl) 0.98 Å with Uiso = 1.5Ueq(C) and in (5) only, N—H, 0.88 Å, with Uiso = 1.2Ueq(C). The positions of the methyl groups were checked on a final difference map as was that of the N—H hydrogen atom in (5). In (4), the high difference map peaks were associated with the Br atom.
details are summarized in Table 12
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Supporting information
10.1107/S2056989016001833/hb7562sup1.cif
contains datablocks 1, 2, 3, 4, 5, global. DOI:Structure factors: contains datablock 1. DOI: 10.1107/S2056989016001833/hb75621sup2.hkl
Structure factors: contains datablock 2. DOI: 10.1107/S2056989016001833/hb75622sup3.hkl
Structure factors: contains datablock 3. DOI: 10.1107/S2056989016001833/hb75623sup4.hkl
Structure factors: contains datablock 4. DOI: 10.1107/S2056989016001833/hb75624sup5.hkl
Structure factors: contains datablock 5. DOI: 10.1107/S2056989016001833/hb75625sup6.hkl
Supporting information file. DOI: 10.1107/S2056989016001833/hb75621sup7.cml
Supporting information file. DOI: 10.1107/S2056989016001833/hb75622sup8.cml
Supporting information file. DOI: 10.1107/S2056989016001833/hb75623sup9.cml
Supporting information file. DOI: 10.1107/S2056989016001833/hb75624sup10.cml
Supporting information file. DOI: 10.1107/S2056989016001833/hb75625sup11.cml
Purines, purine
and their analogs, are nitrogen-containing heterocycles ubiquitous in nature and present in biological systems like man, plants and marine organisms (Legraverend, 2008). These types of heterocycles take part of the core structure of guanine and adenine in (DNA and RNA) being involved in diverse in vivo catabolic and anabolic metabolic pathways.6-Mercaptopurine is a water insoluble purine analogue, which attracted attention due to its antitumor and immunosuppressive properties. The drug is used, among others, in the treatment of rheumathologic disorders, cancer and prevention of rejection of organ transplantation. The main problem associated with the pharmacological treatment with 6-mercaptopurine is the low bioavailability of the oral absorption and the short half-life in plasma. Strategies that have been adopted to circumvent those problems include the administration of 6-mercaptopurine analogous that act as prodrugs or by the chemical protection of the thiol group.
Chemically, the 6-mercaptopurine scaffold can also be modulated by an appropriate selection of the substituents that can be located at C-2, N-1, C-6, N-3, C-8, N-7 and N-9 positions, generating a variety of derivatives with potential biological applications (Legraverend & Grierson, 2006; Tunçbilek, et al., 2009).
Within this framework, the goal of this project has been focused on the functionalization of 6-mercapto purine at positions 6 and 9. Here we describe the syntheses and characterization of five 6-mercaptopurine derivatives: 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(3-methoxyphenyl)ethan-1-one (1), 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-methoxyphenyl)ethan-1-one (2), 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-chlorophenyl)ethan-1-one (3), 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-bromophenyl)ethan-1-one (4) and 1-(3-methoxyphenyl)-2-[(9H-purin-6-yl)sulfanyl]ethan-1-one (5).
Compounds (1)–(5) are shown in the scheme and their ellipsoid plots are shown in Figs. 1–5. Compounds (1) and (5) have similar a and c axes and (2), (3) and (4) are isostructural and isomorphous.
These compounds can be envisaged as two building blocks, a substituted phenylethanone grouping and a substituted 6-mercaptopurine moiety, bonded together by the mercapto ethanone residue. Since both purine and phenyl rings are essentially planar, the structural conformations of those compounds are conditioned by the –SCH2CO spacer (Fig. 6) which permits rotations around the following bonds: Pu—S6, S6—C61, C61—C62 and C62—Ph bonds. The sp3 character of the central carbon atom may also direct the relative positions of the acetophenone residue out of the main plane constituted by the mercaptopurine, which is not the case of the present compounds. Selected geometric parameters for compounds (1)–(5) are given in Tables 1–5, respectively.
The Pu—S6 bond tends to be coplanar with the purine residue. In fact, the 6-mercaptopurine itself may appear in the thione form, e.g. 3,7-dihydropurine-6-thione, as a consequence of the high degree of electron delocalization within the 6-mercaptopurine environment. The tendency for the Pu—S6 bond to assume partial double-bond character is also seen in the present compounds, for which the corresponding Pu—S6 bond lengths lie between 1.741 (3) Å for (2) and 1.755 (3) Å for (4). In contrast, the S6—C61 bond lengths are longer, with values lying between 1.8017 (18) Å in (1) and 1.812 (3) Å in (4). This bond can also be bent with respect to the main mercaptopurine plane. The degree of bending may be evaluated by the distance of the C62 carbon atom from the mean plane consisting of the mercaptopyrimidine atoms. Those values [0.307 (3), 0.272 (4), 0.333 (2), 0.332 (4) and 0.164 (2) for (1)–(5), respectively] show that the degree of bending is higher in (1)–(4) than in (5). As regards the ethanone group, the C61—C62 bond lengths lie in the range 1.510 (4) Å (2) to 1.528 (4) Å, (4) and are normal for a Csp3—Csp3 bond while the C62—Ph bond lengths are shorter and lie in the range 1.474 (3) Å (2) to 1.496 (4) (4), suggesting that the electron density is delocalized from the phenyl ring.
The dihedral angles between the mean planes of the of the purine and phenyl ring, θ1, those between the mean plane of the purine ring and the plane defined by the S6—C61—C62—O6 atoms, θ2, and those between the mean planes of the phenyl ring and the plane defined by the S6—C61—C62—O6 atoms, θ3 are given in Table 6. These values show that the molecules of (1) and (5) are essentially planar. However, in the case of the three isomorphous compounds (2), (3) and (4), the purine and exocyclic phenyl rings are both twisted in the opposite direction from the plane of the bridging unit, resulting in a dihedral angle of approximately 38°. This is due to the rotations and bending around the bonds connecting the bridging unit to the purine and exocyclic phenyl rings as discussed above. The dihedral angles θ2 are higher than θ3; the former are mainly due to the rotations around the S6—C61 bond while the latter are mainly the result of the bending of the C62—Ph bond.
There are no weak C—H···O or C—H···N contacts in (1). Hydrogen bonds for (2)–(5) are listed in Tables 7–10, respectively. Since (2), (3) and (4) are isomorphous, their supramolecular structures follow similar patterns. Accordingly, hydrogen-bonding diagrams are given for (2) only. Atom C8 acts as a donor to O9 (−x − 1, −y + 1, −z + 1), via H8 forming an R22(10) centrosymmetric dimer across the inversion centre at (−1/2, 1/2, 1/2), Fig. 7. Atom C61 makes a hydrogen bond with O6 (−x + 1, y + 1/2, −z + 1/2), via H61A, forming a C4 chain which runs parallel to the b axis, Fig. 8, generated by the twofold screw axis at (1/2, y, 1/4). In (2), there is a short contact between C6 and the 4-methoxy atom O64 (−x + 2, y + 1/2, −z + 1/2), forming a C12 chain which runs parallel to the b axis and is generated by the twofold screw axis at (1, y, 1/4). In (5), the N9—H9···N9 (x − 1/2, −y + 1/2, z − 1/2) hydrogen bond links the molecules into a C4 chain which runs parallel to [101] and which is generated by the n-glide plane at (0, 1/4, 0).
Since those compounds have three rings, the imidazole ring (with centroid Cg1), the pyrimidine ring (with centroid Cg2) and the benzyl ring (with centroid Cg3), it would be expected that π–π contacts were part of the supramolecular structure. Table 11 lists the possible π–π contacts for (1)–(5). As may be seen in the Table, the pyrimidine ring establishes π–π contacts with the benzyl ring for all compounds. In (1), two molecules centrosymmetrically related across the inversion centre at (0, 1/2, 1/2) are involved in π–π stacking in which the purine ring stacks above the exocyclic phenyl ring. In (2), (3) and (4), the π–π stacking is between imidazole rings while in (1) and (5), the contact is between an imidazole ring and a benzyl ring. In particular, in (1) and (5) two molecules centrosymmetrically related across the centre of symmetry at (0, 1/2, 1/2) are involved in π–π stacking in which the purine rings stack above the exocyclic phenyl ring, Table 11.
\ A search made in the Cambridge Structural Database (Groom & Allen, 2014) revealed the existence of 11 deposited compounds containing the 2-thio-1-phenylethanone scaffold (see supplementary Figure). Of those, only eight have a cyclic ring as substituent, the majority of these being heterocycles: MUCCUJ: 2-(1,3-benzoxazol-2-ylsulfanyl)-1-phenylethanone (Loghmani-Khouzani et al., 2009a); NENFAO: 3-(benzoylmethylthio)-1,5-diphenyl-1H-1,2,4-triazole (Liu et al., 2006); PUFGED: 2-(1,3-benzothiazol-2-ylsulfanyl)-1-phenylethanone (Loghmani-Khouzani et al., 2009b); IKAXOI: 6-cyclohexylmethyl-5-ethyl-2-[(2-oxo-2-phenylethyl)sulfanyl]pyrimidin-\ 4(3H)-οne (Yan et al., 2011); SILGAW: 2-(benzoylmethylsulfanyl)-6-benzyl-5-isopropylpyrimidin-4(3H)-one (Rao et al., 2007); ETEWOP: 2-(benzoylmethylsulphanyl)-6-methoxy-1H-benzamide (Lynch & McLenaghan, 2004); XEBWEI: 2-(1,3-benzimidazolol-2-ylsulfanyl)phenylethanone (Abdel-Aziz et al., 2012); UGITUA: 2-[(4-methoxybenzyl)sulfanyl]-1-phenylethanone (Heravi et al., 2009).
The R—S bond distances for these compounds are similar to those of the studied compounds and they assume a partial double-bond character with the exception of UGITUA where the S atom is bonded to a phenyl ring, suggesting a tendency for delocalization of the electron density through the sulfur atom when the ring has heteroatoms. The S—CH2 bond distances vary between 1.80 and 1.81 Å with exception of SILGAW (1.79 Å) and ETEWOP (1.82 Å). The supplementary figure also gives information about the distances of the –CH2– carbon atom to the best plane made up of the atoms of the heterocycles (CH2– distance). These values were computed in order to evaluate the degree of bending of the S—CH2 bond with respect to the main plane of the substituted rings. There are two main groups of compounds, one in which the distance is shorter than 0.3 Å and the other, which contains the CNH fragment in the heterocyclic ring, in which this distance is greater than 1.2 Å. As noted above, the sp3 character of the β-carbon atom of the ethanone fragment may also direct the relative positions of the acetophenone residue out of the main plane constituted by the substituted heteroaromatic ring. This is the case for SILGAW and IKAXOI. Thus, despite the small sample size, there is a wide range of adopted conformations.
The 6-mercaptopurine derivatives (1)–(5) were obtained in moderate yields by a two-step synthetic strategy. Firstly, 6-mercaptopurine was alkylated using diverse monobromide acetophenone derivatives in DMF/potassium carbonate medium at room temperature (Lambertucci, et al. 2009). After thiol alkylation, the purine nucleus was acylated in position 9 with acetic anhydride in triethylamine and anhydrous DMF for (1)–(4) under an argon atmosphere at room temperature (Masai, et al. 2002). All compounds were recrystallized from dichloromethane solution: 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(3-methoxyphenyl)ethan-1-one (1): overall yield: 48%; m.p. 432–435 K; 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-methoxyphenyl)ethan-1-one (2): overall yield: 17%; m.p. 460–463 K; 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-chlorophenyl)ethan-1-one (3): overall yield: 26%; m.p. 453–457 K; 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-bromophenyl)ethan-1-one (4): overall yield: 10%; m.p. 449–451 K; 1-(3-methoxyphenyl)-2-[(9H-purin-6-yl)sulfanyl]ethan-1-one (5): overall yield: 55%; m.p. 461–464 K.
Crystal data, data collection and structure
details are summarized in Table 2. H atoms were treated as riding atoms with C—H(aromatic), 0.95 Å, with Uiso = 1.2Ueq(C), C—H2(methylene), 0.99 Å, with Uiso = 1.2Ueq(C),C—H(methyl) 0.98 Å with Uiso = 1.5Ueq(C) and in (5) only, N—H, 0.88 Å, with Uiso = 1.2Ueq(C). The positions of the methyl groups were checked on a final difference map as was that of the N—H hydrogen atom in (5). In (4), the high difference map peaks were associated with the Br atom.Purines, purine
and their analogs, are nitrogen-containing heterocycles ubiquitous in nature and present in biological systems like man, plants and marine organisms (Legraverend, 2008). These types of heterocycles take part of the core structure of guanine and adenine in (DNA and RNA) being involved in diverse in vivo catabolic and anabolic metabolic pathways.6-Mercaptopurine is a water insoluble purine analogue, which attracted attention due to its antitumor and immunosuppressive properties. The drug is used, among others, in the treatment of rheumathologic disorders, cancer and prevention of rejection of organ transplantation. The main problem associated with the pharmacological treatment with 6-mercaptopurine is the low bioavailability of the oral absorption and the short half-life in plasma. Strategies that have been adopted to circumvent those problems include the administration of 6-mercaptopurine analogous that act as prodrugs or by the chemical protection of the thiol group.
Chemically, the 6-mercaptopurine scaffold can also be modulated by an appropriate selection of the substituents that can be located at C-2, N-1, C-6, N-3, C-8, N-7 and N-9 positions, generating a variety of derivatives with potential biological applications (Legraverend & Grierson, 2006; Tunçbilek, et al., 2009).
Within this framework, the goal of this project has been focused on the functionalization of 6-mercapto purine at positions 6 and 9. Here we describe the syntheses and characterization of five 6-mercaptopurine derivatives: 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(3-methoxyphenyl)ethan-1-one (1), 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-methoxyphenyl)ethan-1-one (2), 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-chlorophenyl)ethan-1-one (3), 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-bromophenyl)ethan-1-one (4) and 1-(3-methoxyphenyl)-2-[(9H-purin-6-yl)sulfanyl]ethan-1-one (5).
Compounds (1)–(5) are shown in the scheme and their ellipsoid plots are shown in Figs. 1–5. Compounds (1) and (5) have similar a and c axes and (2), (3) and (4) are isostructural and isomorphous.
These compounds can be envisaged as two building blocks, a substituted phenylethanone grouping and a substituted 6-mercaptopurine moiety, bonded together by the mercapto ethanone residue. Since both purine and phenyl rings are essentially planar, the structural conformations of those compounds are conditioned by the –SCH2CO spacer (Fig. 6) which permits rotations around the following bonds: Pu—S6, S6—C61, C61—C62 and C62—Ph bonds. The sp3 character of the central carbon atom may also direct the relative positions of the acetophenone residue out of the main plane constituted by the mercaptopurine, which is not the case of the present compounds. Selected geometric parameters for compounds (1)–(5) are given in Tables 1–5, respectively.
The Pu—S6 bond tends to be coplanar with the purine residue. In fact, the 6-mercaptopurine itself may appear in the thione form, e.g. 3,7-dihydropurine-6-thione, as a consequence of the high degree of electron delocalization within the 6-mercaptopurine environment. The tendency for the Pu—S6 bond to assume partial double-bond character is also seen in the present compounds, for which the corresponding Pu—S6 bond lengths lie between 1.741 (3) Å for (2) and 1.755 (3) Å for (4). In contrast, the S6—C61 bond lengths are longer, with values lying between 1.8017 (18) Å in (1) and 1.812 (3) Å in (4). This bond can also be bent with respect to the main mercaptopurine plane. The degree of bending may be evaluated by the distance of the C62 carbon atom from the mean plane consisting of the mercaptopyrimidine atoms. Those values [0.307 (3), 0.272 (4), 0.333 (2), 0.332 (4) and 0.164 (2) for (1)–(5), respectively] show that the degree of bending is higher in (1)–(4) than in (5). As regards the ethanone group, the C61—C62 bond lengths lie in the range 1.510 (4) Å (2) to 1.528 (4) Å, (4) and are normal for a Csp3—Csp3 bond while the C62—Ph bond lengths are shorter and lie in the range 1.474 (3) Å (2) to 1.496 (4) (4), suggesting that the electron density is delocalized from the phenyl ring.
The dihedral angles between the mean planes of the of the purine and phenyl ring, θ1, those between the mean plane of the purine ring and the plane defined by the S6—C61—C62—O6 atoms, θ2, and those between the mean planes of the phenyl ring and the plane defined by the S6—C61—C62—O6 atoms, θ3 are given in Table 6. These values show that the molecules of (1) and (5) are essentially planar. However, in the case of the three isomorphous compounds (2), (3) and (4), the purine and exocyclic phenyl rings are both twisted in the opposite direction from the plane of the bridging unit, resulting in a dihedral angle of approximately 38°. This is due to the rotations and bending around the bonds connecting the bridging unit to the purine and exocyclic phenyl rings as discussed above. The dihedral angles θ2 are higher than θ3; the former are mainly due to the rotations around the S6—C61 bond while the latter are mainly the result of the bending of the C62—Ph bond.
There are no weak C—H···O or C—H···N contacts in (1). Hydrogen bonds for (2)–(5) are listed in Tables 7–10, respectively. Since (2), (3) and (4) are isomorphous, their supramolecular structures follow similar patterns. Accordingly, hydrogen-bonding diagrams are given for (2) only. Atom C8 acts as a donor to O9 (−x − 1, −y + 1, −z + 1), via H8 forming an R22(10) centrosymmetric dimer across the inversion centre at (−1/2, 1/2, 1/2), Fig. 7. Atom C61 makes a hydrogen bond with O6 (−x + 1, y + 1/2, −z + 1/2), via H61A, forming a C4 chain which runs parallel to the b axis, Fig. 8, generated by the twofold screw axis at (1/2, y, 1/4). In (2), there is a short contact between C6 and the 4-methoxy atom O64 (−x + 2, y + 1/2, −z + 1/2), forming a C12 chain which runs parallel to the b axis and is generated by the twofold screw axis at (1, y, 1/4). In (5), the N9—H9···N9 (x − 1/2, −y + 1/2, z − 1/2) hydrogen bond links the molecules into a C4 chain which runs parallel to [101] and which is generated by the n-glide plane at (0, 1/4, 0).
Since those compounds have three rings, the imidazole ring (with centroid Cg1), the pyrimidine ring (with centroid Cg2) and the benzyl ring (with centroid Cg3), it would be expected that π–π contacts were part of the supramolecular structure. Table 11 lists the possible π–π contacts for (1)–(5). As may be seen in the Table, the pyrimidine ring establishes π–π contacts with the benzyl ring for all compounds. In (1), two molecules centrosymmetrically related across the inversion centre at (0, 1/2, 1/2) are involved in π–π stacking in which the purine ring stacks above the exocyclic phenyl ring. In (2), (3) and (4), the π–π stacking is between imidazole rings while in (1) and (5), the contact is between an imidazole ring and a benzyl ring. In particular, in (1) and (5) two molecules centrosymmetrically related across the centre of symmetry at (0, 1/2, 1/2) are involved in π–π stacking in which the purine rings stack above the exocyclic phenyl ring, Table 11.
\ A search made in the Cambridge Structural Database (Groom & Allen, 2014) revealed the existence of 11 deposited compounds containing the 2-thio-1-phenylethanone scaffold (see supplementary Figure). Of those, only eight have a cyclic ring as substituent, the majority of these being heterocycles: MUCCUJ: 2-(1,3-benzoxazol-2-ylsulfanyl)-1-phenylethanone (Loghmani-Khouzani et al., 2009a); NENFAO: 3-(benzoylmethylthio)-1,5-diphenyl-1H-1,2,4-triazole (Liu et al., 2006); PUFGED: 2-(1,3-benzothiazol-2-ylsulfanyl)-1-phenylethanone (Loghmani-Khouzani et al., 2009b); IKAXOI: 6-cyclohexylmethyl-5-ethyl-2-[(2-oxo-2-phenylethyl)sulfanyl]pyrimidin-\ 4(3H)-οne (Yan et al., 2011); SILGAW: 2-(benzoylmethylsulfanyl)-6-benzyl-5-isopropylpyrimidin-4(3H)-one (Rao et al., 2007); ETEWOP: 2-(benzoylmethylsulphanyl)-6-methoxy-1H-benzamide (Lynch & McLenaghan, 2004); XEBWEI: 2-(1,3-benzimidazolol-2-ylsulfanyl)phenylethanone (Abdel-Aziz et al., 2012); UGITUA: 2-[(4-methoxybenzyl)sulfanyl]-1-phenylethanone (Heravi et al., 2009).
The R—S bond distances for these compounds are similar to those of the studied compounds and they assume a partial double-bond character with the exception of UGITUA where the S atom is bonded to a phenyl ring, suggesting a tendency for delocalization of the electron density through the sulfur atom when the ring has heteroatoms. The S—CH2 bond distances vary between 1.80 and 1.81 Å with exception of SILGAW (1.79 Å) and ETEWOP (1.82 Å). The supplementary figure also gives information about the distances of the –CH2– carbon atom to the best plane made up of the atoms of the heterocycles (CH2– distance). These values were computed in order to evaluate the degree of bending of the S—CH2 bond with respect to the main plane of the substituted rings. There are two main groups of compounds, one in which the distance is shorter than 0.3 Å and the other, which contains the CNH fragment in the heterocyclic ring, in which this distance is greater than 1.2 Å. As noted above, the sp3 character of the β-carbon atom of the ethanone fragment may also direct the relative positions of the acetophenone residue out of the main plane constituted by the substituted heteroaromatic ring. This is the case for SILGAW and IKAXOI. Thus, despite the small sample size, there is a wide range of adopted conformations.
The 6-mercaptopurine derivatives (1)–(5) were obtained in moderate yields by a two-step synthetic strategy. Firstly, 6-mercaptopurine was alkylated using diverse monobromide acetophenone derivatives in DMF/potassium carbonate medium at room temperature (Lambertucci, et al. 2009). After thiol alkylation, the purine nucleus was acylated in position 9 with acetic anhydride in triethylamine and anhydrous DMF for (1)–(4) under an argon atmosphere at room temperature (Masai, et al. 2002). All compounds were recrystallized from dichloromethane solution: 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(3-methoxyphenyl)ethan-1-one (1): overall yield: 48%; m.p. 432–435 K; 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-methoxyphenyl)ethan-1-one (2): overall yield: 17%; m.p. 460–463 K; 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-chlorophenyl)ethan-1-one (3): overall yield: 26%; m.p. 453–457 K; 2-[(9-acetyl-9H-purin-6-yl)sulfanyl]-1-(4-bromophenyl)ethan-1-one (4): overall yield: 10%; m.p. 449–451 K; 1-(3-methoxyphenyl)-2-[(9H-purin-6-yl)sulfanyl]ethan-1-one (5): overall yield: 55%; m.p. 461–464 K.
detailsCrystal data, data collection and structure
details are summarized in Table 2. H atoms were treated as riding atoms with C—H(aromatic), 0.95 Å, with Uiso = 1.2Ueq(C), C—H2(methylene), 0.99 Å, with Uiso = 1.2Ueq(C),C—H(methyl) 0.98 Å with Uiso = 1.5Ueq(C) and in (5) only, N—H, 0.88 Å, with Uiso = 1.2Ueq(C). The positions of the methyl groups were checked on a final difference map as was that of the N—H hydrogen atom in (5). In (4), the high difference map peaks were associated with the Br atom.Data collection: CrystalClear-SM Expert (Rigaku, 2012) for (1), (3), (4), (5); CrysAlis PRO (Agilent, 2014) for (2). Cell
CrystalClear-SM Expert (Rigaku, 2012) for (1), (3), (4), (5); CrysAlis PRO (Agilent, 2014) for (2). Data reduction: CrystalClear-SM Expert (Rigaku, 2012) for (1), (3), (4), (5); CrysAlis PRO (Agilent, 2014) for (2). For all compounds, program(s) used to solve structure: OSCAIL (McArdle et al., 2004) and SHELXT (Sheldrick, 2015a); program(s) used to refine structure: OSCAIL (McArdle et al., 2004), ShelXle (Hübschle et al., 2011) and SHELXL2014 (Sheldrick, 2015b); 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).Fig. 1. A view of the asymmetric unit of (1), with displacement ellipsoids are drawn at the 70% probability level. | |
Fig. 2. A view of the asymmetric unit of (2), with displacement ellipsoids are drawn at the 70% probability level. | |
Fig. 3. A view of the asymmetric unit of (3), with displacement ellipsoids are drawn at the 70% probability level. | |
Fig. 4. A view of the asymmetric unit of (4), with displacement ellipsoids are drawn at the 70% probability level. | |
Fig. 5. A view of the asymmetric unit of (5), with displacement ellipsoids are drawn at the 70% probability level. | |
Fig. 6. Diagram of the S–CH2–C(═O)– linkage. | |
Fig. 7. Compound (2): view of the C8—H8···O9 centrosymetric R22(16) ring structure centred on (−1/2, 1/2, 1/2). Symmetry code: (i) −x − 1, −y + 1, −z + 1. H atoms not involved in the hydrogen bonding are omitted. | |
Fig. 8. Compound (2): the simple C4 chain formed by the C61—H61A···O6 weak hydrogen bond. This chain extends along the b axis and is generated by the twofold screw axis at (1/2, y, 1/4). Symmetry codes: (i) −x + 1, y + 1/2, −z + 1/2; (ii) −x +???, y − 1/2, −z + 1/2. H atoms not involved in the hydrogen bonding are omitted. | |
Fig. 9. Compound (2): the simple C12 chain formed by the C2—H2···O64 weak hydrogen bond. This chain extends along the b axis and is generated by the twofold screw-axis at (1, y, 1/4). Symmetry codes: (i) −x + 2, y + 1/2, −z + 1/2; (ii) −x + 2, y − 1/2, −z + 1/2. H atoms not involved in the hydrogen bonding are omitted. | |
Fig. 10. Compound (5): the simple C4 chain formed by the N9—H9···O64 weak hydrogen bond. This chain extends along the b axis and is generated by the n-glide plane at (0, 1/4, 0). Symmetry codes: (i) x − 1/2, −y + 1/2, −z − 1/2; (ii) x − 1/2, −y + 1/2, −z + 1/2. H atoms not involved in the hydrogen bonding are omitted. |
C16H14N4O3S | F(000) = 712 |
Mr = 342.37 | Dx = 1.513 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
a = 7.6343 (5) Å | Cell parameters from 18327 reflections |
b = 26.2356 (18) Å | θ = 2.7–27.5° |
c = 8.1332 (5) Å | µ = 0.24 mm−1 |
β = 112.725 (2)° | T = 100 K |
V = 1502.54 (17) Å3 | Plate, orange |
Z = 4 | 0.17 × 0.07 × 0.01 mm |
Rigaku AFC12 (Right) diffractometer | 3450 independent reflections |
Radiation source: Rotating Anode | 2817 reflections with I > 2σ(I) |
Detector resolution: 28.5714 pixels mm-1 | Rint = 0.089 |
profile data from ω–scans | θmax = 27.5°, θmin = 2.8° |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 20112) | h = −9→9 |
Tmin = 0, Tmax = 1.000 | k = −33→34 |
20144 measured reflections | l = −10→10 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.148 | w = 1/[σ2(Fo2) + (0.0878P)2 + 0.318P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
3450 reflections | Δρmax = 0.81 e Å−3 |
219 parameters | Δρmin = −0.51 e Å−3 |
C16H14N4O3S | V = 1502.54 (17) Å3 |
Mr = 342.37 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.6343 (5) Å | µ = 0.24 mm−1 |
b = 26.2356 (18) Å | T = 100 K |
c = 8.1332 (5) Å | 0.17 × 0.07 × 0.01 mm |
β = 112.725 (2)° |
Rigaku AFC12 (Right) diffractometer | 3450 independent reflections |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 20112) | 2817 reflections with I > 2σ(I) |
Tmin = 0, Tmax = 1.000 | Rint = 0.089 |
20144 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.81 e Å−3 |
3450 reflections | Δρmin = −0.51 e Å−3 |
219 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S6 | 0.32576 (7) | 0.51901 (2) | 0.60919 (6) | 0.03400 (17) | |
O6 | 0.24518 (19) | 0.61509 (5) | 0.4576 (2) | 0.0421 (4) | |
O9 | 0.8227 (2) | 0.31676 (6) | 1.1619 (2) | 0.0427 (4) | |
O63 | −0.20860 (19) | 0.72411 (5) | −0.05304 (18) | 0.0376 (3) | |
N1 | 0.2055 (2) | 0.42325 (6) | 0.4964 (2) | 0.0331 (4) | |
N3 | 0.3481 (2) | 0.34590 (6) | 0.6538 (2) | 0.0323 (4) | |
N7 | 0.6212 (2) | 0.44997 (6) | 0.9142 (2) | 0.0340 (4) | |
N9 | 0.6216 (2) | 0.36406 (6) | 0.9348 (2) | 0.0325 (4) | |
C2 | 0.2207 (3) | 0.37227 (7) | 0.5197 (3) | 0.0342 (4) | |
H2 | 0.1291 | 0.3525 | 0.4292 | 0.041* | |
C4 | 0.4710 (3) | 0.37649 (7) | 0.7754 (3) | 0.0309 (4) | |
C5 | 0.4740 (3) | 0.42955 (7) | 0.7676 (2) | 0.0312 (4) | |
C6 | 0.3330 (3) | 0.45263 (7) | 0.6203 (2) | 0.0308 (4) | |
C8 | 0.7025 (3) | 0.41060 (7) | 1.0084 (3) | 0.0343 (4) | |
H8 | 0.8086 | 0.4132 | 1.1185 | 0.041* | |
C9 | 0.6911 (3) | 0.31650 (7) | 1.0206 (3) | 0.0344 (4) | |
C61 | 0.1558 (3) | 0.52851 (7) | 0.3849 (2) | 0.0321 (4) | |
H61A | 0.1996 | 0.5115 | 0.2989 | 0.039* | |
H61B | 0.0313 | 0.5139 | 0.3711 | 0.039* | |
C62 | 0.1376 (3) | 0.58558 (7) | 0.3504 (3) | 0.0322 (4) | |
C91 | 0.5932 (3) | 0.26954 (7) | 0.9240 (3) | 0.0396 (5) | |
H91A | 0.6527 | 0.2394 | 0.9945 | 0.059* | |
H91B | 0.6040 | 0.2678 | 0.8080 | 0.059* | |
H91C | 0.4588 | 0.2707 | 0.9064 | 0.059* | |
C631 | −0.0135 (2) | 0.60328 (7) | 0.1806 (2) | 0.0312 (4) | |
C632 | −0.0336 (3) | 0.65606 (7) | 0.1486 (2) | 0.0317 (4) | |
H632 | 0.0474 | 0.6794 | 0.2332 | 0.038* | |
C633 | −0.1734 (3) | 0.67364 (7) | −0.0084 (3) | 0.0328 (4) | |
C634 | −0.2922 (3) | 0.63923 (8) | −0.1321 (3) | 0.0361 (4) | |
H634 | −0.3883 | 0.6514 | −0.2390 | 0.043* | |
C635 | −0.2701 (3) | 0.58745 (8) | −0.0994 (3) | 0.0373 (4) | |
H635 | −0.3502 | 0.5642 | −0.1849 | 0.045* | |
C636 | −0.1321 (3) | 0.56914 (7) | 0.0572 (3) | 0.0352 (4) | |
H636 | −0.1188 | 0.5335 | 0.0798 | 0.042* | |
C637 | −0.0942 (3) | 0.76081 (7) | 0.0721 (3) | 0.0396 (5) | |
H63A | 0.0390 | 0.7563 | 0.0885 | 0.059* | |
H63B | −0.1070 | 0.7561 | 0.1864 | 0.059* | |
H63C | −0.1362 | 0.7952 | 0.0271 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S6 | 0.0278 (3) | 0.0304 (3) | 0.0354 (3) | 0.00002 (17) | 0.0030 (2) | −0.00035 (17) |
O6 | 0.0327 (7) | 0.0341 (7) | 0.0442 (8) | −0.0027 (6) | −0.0019 (6) | 0.0004 (6) |
O9 | 0.0351 (8) | 0.0417 (8) | 0.0422 (8) | 0.0012 (6) | 0.0048 (7) | 0.0043 (6) |
O63 | 0.0322 (7) | 0.0346 (7) | 0.0376 (7) | 0.0025 (5) | 0.0042 (6) | 0.0021 (5) |
N1 | 0.0283 (8) | 0.0332 (8) | 0.0347 (8) | −0.0007 (6) | 0.0088 (6) | −0.0002 (6) |
N3 | 0.0280 (8) | 0.0333 (8) | 0.0337 (8) | −0.0013 (6) | 0.0097 (7) | −0.0008 (6) |
N7 | 0.0244 (8) | 0.0361 (8) | 0.0368 (9) | −0.0011 (6) | 0.0066 (7) | −0.0020 (6) |
N9 | 0.0241 (8) | 0.0344 (8) | 0.0358 (8) | 0.0015 (6) | 0.0080 (7) | 0.0013 (6) |
C2 | 0.0303 (9) | 0.0347 (9) | 0.0341 (10) | −0.0021 (7) | 0.0087 (8) | −0.0023 (7) |
C4 | 0.0236 (8) | 0.0342 (9) | 0.0336 (9) | 0.0014 (7) | 0.0096 (7) | 0.0008 (7) |
C5 | 0.0240 (8) | 0.0324 (9) | 0.0341 (9) | 0.0000 (7) | 0.0080 (7) | −0.0005 (7) |
C6 | 0.0261 (9) | 0.0309 (9) | 0.0342 (9) | 0.0002 (7) | 0.0102 (8) | −0.0010 (7) |
C8 | 0.0246 (8) | 0.0378 (10) | 0.0366 (10) | −0.0017 (7) | 0.0076 (8) | −0.0022 (8) |
C9 | 0.0280 (9) | 0.0367 (10) | 0.0389 (10) | 0.0029 (7) | 0.0133 (8) | 0.0033 (8) |
C61 | 0.0246 (9) | 0.0324 (9) | 0.0331 (10) | −0.0005 (7) | 0.0041 (7) | 0.0007 (7) |
C62 | 0.0245 (8) | 0.0342 (9) | 0.0344 (9) | −0.0009 (7) | 0.0077 (7) | −0.0003 (7) |
C91 | 0.0345 (10) | 0.0368 (10) | 0.0442 (11) | 0.0011 (8) | 0.0115 (9) | 0.0006 (8) |
C631 | 0.0231 (8) | 0.0362 (9) | 0.0329 (9) | 0.0000 (7) | 0.0092 (7) | 0.0010 (7) |
C632 | 0.0249 (9) | 0.0343 (9) | 0.0326 (9) | −0.0007 (7) | 0.0076 (7) | −0.0003 (7) |
C633 | 0.0260 (9) | 0.0360 (9) | 0.0351 (10) | 0.0032 (7) | 0.0103 (8) | 0.0028 (7) |
C634 | 0.0266 (9) | 0.0455 (11) | 0.0318 (10) | 0.0024 (8) | 0.0065 (8) | 0.0014 (8) |
C635 | 0.0290 (9) | 0.0423 (10) | 0.0357 (10) | −0.0043 (8) | 0.0072 (8) | −0.0058 (8) |
C636 | 0.0301 (9) | 0.0349 (9) | 0.0374 (10) | −0.0014 (7) | 0.0096 (8) | −0.0007 (7) |
C637 | 0.0346 (10) | 0.0351 (10) | 0.0425 (11) | 0.0010 (8) | 0.0075 (9) | 0.0011 (8) |
S6—C6 | 1.7438 (19) | C61—C62 | 1.520 (3) |
S6—C61 | 1.8017 (18) | C61—H61A | 0.9900 |
O6—C62 | 1.217 (2) | C61—H61B | 0.9900 |
O9—C9 | 1.199 (2) | C62—C631 | 1.491 (3) |
O63—C633 | 1.372 (2) | C91—H91A | 0.9800 |
O63—C637 | 1.428 (2) | C91—H91B | 0.9800 |
N1—C6 | 1.341 (2) | C91—H91C | 0.9800 |
N1—C2 | 1.350 (2) | C631—C636 | 1.388 (3) |
N3—C4 | 1.336 (2) | C631—C632 | 1.407 (3) |
N3—C2 | 1.340 (2) | C632—C633 | 1.389 (3) |
N7—C8 | 1.293 (2) | C632—H632 | 0.9500 |
N7—C5 | 1.392 (2) | C633—C634 | 1.395 (3) |
N9—C8 | 1.395 (2) | C634—C635 | 1.382 (3) |
N9—C4 | 1.399 (2) | C634—H634 | 0.9500 |
N9—C9 | 1.428 (2) | C635—C636 | 1.388 (3) |
C2—H2 | 0.9500 | C635—H635 | 0.9500 |
C4—C5 | 1.394 (3) | C636—H636 | 0.9500 |
C5—C6 | 1.401 (2) | C637—H63A | 0.9800 |
C8—H8 | 0.9500 | C637—H63B | 0.9800 |
C9—C91 | 1.496 (3) | C637—H63C | 0.9800 |
C6—S6—C61 | 100.76 (9) | O6—C62—C61 | 120.45 (17) |
C633—O63—C637 | 117.31 (15) | C631—C62—C61 | 117.42 (15) |
C6—N1—C2 | 117.76 (16) | C9—C91—H91A | 109.5 |
C4—N3—C2 | 111.95 (16) | C9—C91—H91B | 109.5 |
C8—N7—C5 | 104.13 (16) | H91A—C91—H91B | 109.5 |
C8—N9—C4 | 105.22 (15) | C9—C91—H91C | 109.5 |
C8—N9—C9 | 122.41 (16) | H91A—C91—H91C | 109.5 |
C4—N9—C9 | 132.36 (16) | H91B—C91—H91C | 109.5 |
N3—C2—N1 | 128.47 (17) | C636—C631—C632 | 120.49 (17) |
N3—C2—H2 | 115.8 | C636—C631—C62 | 121.58 (17) |
N1—C2—H2 | 115.8 | C632—C631—C62 | 117.92 (16) |
N3—C4—C5 | 125.80 (17) | C633—C632—C631 | 119.17 (17) |
N3—C4—N9 | 129.53 (17) | C633—C632—H632 | 120.4 |
C5—C4—N9 | 104.66 (16) | C631—C632—H632 | 120.4 |
N7—C5—C4 | 111.55 (16) | O63—C633—C632 | 124.49 (17) |
N7—C5—C6 | 131.72 (17) | O63—C633—C634 | 115.30 (16) |
C4—C5—C6 | 116.73 (16) | C632—C633—C634 | 120.20 (17) |
N1—C6—C5 | 119.27 (16) | C635—C634—C633 | 120.01 (18) |
N1—C6—S6 | 122.38 (14) | C635—C634—H634 | 120.0 |
C5—C6—S6 | 118.31 (14) | C633—C634—H634 | 120.0 |
N7—C8—N9 | 114.43 (17) | C634—C635—C636 | 120.66 (18) |
N7—C8—H8 | 122.8 | C634—C635—H635 | 119.7 |
N9—C8—H8 | 122.8 | C636—C635—H635 | 119.7 |
O9—C9—N9 | 118.60 (18) | C631—C636—C635 | 119.46 (18) |
O9—C9—C91 | 124.84 (18) | C631—C636—H636 | 120.3 |
N9—C9—C91 | 116.55 (17) | C635—C636—H636 | 120.3 |
C62—C61—S6 | 107.55 (12) | O63—C637—H63A | 109.5 |
C62—C61—H61A | 110.2 | O63—C637—H63B | 109.5 |
S6—C61—H61A | 110.2 | H63A—C637—H63B | 109.5 |
C62—C61—H61B | 110.2 | O63—C637—H63C | 109.5 |
S6—C61—H61B | 110.2 | H63A—C637—H63C | 109.5 |
H61A—C61—H61B | 108.5 | H63B—C637—H63C | 109.5 |
O6—C62—C631 | 122.13 (17) | ||
C4—N3—C2—N1 | 0.3 (3) | C9—N9—C8—N7 | −179.35 (18) |
C6—N1—C2—N3 | 0.6 (3) | C8—N9—C9—O9 | 0.7 (3) |
C2—N3—C4—C5 | −1.2 (3) | C4—N9—C9—O9 | −178.2 (2) |
C2—N3—C4—N9 | 178.84 (19) | C8—N9—C9—C91 | −178.60 (18) |
C8—N9—C4—N3 | 179.7 (2) | C4—N9—C9—C91 | 2.5 (3) |
C9—N9—C4—N3 | −1.3 (4) | C6—S6—C61—C62 | −178.05 (13) |
C8—N9—C4—C5 | −0.3 (2) | S6—C61—C62—O6 | 8.5 (2) |
C9—N9—C4—C5 | 178.73 (19) | S6—C61—C62—C631 | −172.56 (14) |
C8—N7—C5—C4 | −0.8 (2) | O6—C62—C631—C636 | 178.23 (19) |
C8—N7—C5—C6 | 178.5 (2) | C61—C62—C631—C636 | −0.7 (3) |
N3—C4—C5—N7 | −179.29 (18) | O6—C62—C631—C632 | −2.1 (3) |
N9—C4—C5—N7 | 0.7 (2) | C61—C62—C631—C632 | 179.03 (17) |
N3—C4—C5—C6 | 1.3 (3) | C636—C631—C632—C633 | −0.2 (3) |
N9—C4—C5—C6 | −178.75 (16) | C62—C631—C632—C633 | −179.87 (17) |
C2—N1—C6—C5 | −0.5 (3) | C637—O63—C633—C632 | −0.7 (3) |
C2—N1—C6—S6 | −178.35 (15) | C637—O63—C633—C634 | 178.19 (18) |
N7—C5—C6—N1 | −179.6 (2) | C631—C632—C633—O63 | 178.91 (17) |
C4—C5—C6—N1 | −0.3 (3) | C631—C632—C633—C634 | 0.1 (3) |
N7—C5—C6—S6 | −1.6 (3) | O63—C633—C634—C635 | −179.39 (18) |
C4—C5—C6—S6 | 177.61 (14) | C632—C633—C634—C635 | −0.5 (3) |
C61—S6—C6—N1 | −12.10 (18) | C633—C634—C635—C636 | 0.9 (3) |
C61—S6—C6—C5 | 170.02 (16) | C632—C631—C636—C635 | 0.6 (3) |
C5—N7—C8—N9 | 0.6 (2) | C62—C631—C636—C635 | −179.72 (18) |
C4—N9—C8—N7 | −0.2 (2) | C634—C635—C636—C631 | −1.0 (3) |
C16H14N4O3S | F(000) = 712 |
Mr = 342.37 | Dx = 1.530 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.9920 (3) Å | Cell parameters from 5825 reflections |
b = 9.9795 (5) Å | θ = 2.2–25.0° |
c = 24.9907 (13) Å | µ = 0.24 mm−1 |
β = 95.977 (5)° | T = 100 K |
V = 1486.25 (13) Å3 | Plate, colourless |
Z = 4 | 0.05 × 0.04 × 0.01 mm |
Rigaku AFC12 (Right) diffractometer | 2619 independent reflections |
Radiation source: Rotating Anode, Rotating Anode | 1852 reflections with I > 2σ(I) |
Confocal mirrors, HF Varimax monochromator | Rint = 0.106 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 25.0°, θmin = 2.2° |
profile data from ω–scans | h = −7→6 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −11→11 |
Tmin = 0.439, Tmax = 1.000 | l = −29→29 |
15437 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0492P)2 + 0.3956P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2619 reflections | Δρmax = 0.30 e Å−3 |
219 parameters | Δρmin = −0.36 e Å−3 |
C16H14N4O3S | V = 1486.25 (13) Å3 |
Mr = 342.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.9920 (3) Å | µ = 0.24 mm−1 |
b = 9.9795 (5) Å | T = 100 K |
c = 24.9907 (13) Å | 0.05 × 0.04 × 0.01 mm |
β = 95.977 (5)° |
Rigaku AFC12 (Right) diffractometer | 2619 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | 1852 reflections with I > 2σ(I) |
Tmin = 0.439, Tmax = 1.000 | Rint = 0.106 |
15437 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.30 e Å−3 |
2619 reflections | Δρmin = −0.36 e Å−3 |
219 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S6 | 0.34226 (12) | 0.45424 (7) | 0.33305 (3) | 0.0300 (2) | |
O6 | 0.6113 (3) | 0.30045 (19) | 0.27249 (7) | 0.0315 (5) | |
O9 | −0.4124 (3) | 0.6642 (2) | 0.51385 (8) | 0.0386 (6) | |
O64 | 1.2947 (3) | 0.54050 (18) | 0.12232 (7) | 0.0331 (5) | |
N1 | 0.3919 (4) | 0.7064 (2) | 0.37258 (9) | 0.0274 (6) | |
N3 | 0.1587 (4) | 0.8075 (2) | 0.43517 (9) | 0.0282 (6) | |
N7 | −0.0486 (4) | 0.4737 (2) | 0.41015 (9) | 0.0295 (6) | |
N9 | −0.1340 (4) | 0.6524 (2) | 0.45982 (8) | 0.0268 (6) | |
C2 | 0.3246 (5) | 0.8061 (3) | 0.40336 (10) | 0.0286 (7) | |
H2 | 0.4069 | 0.8873 | 0.4023 | 0.034* | |
C4 | 0.0500 (4) | 0.6901 (3) | 0.43323 (10) | 0.0260 (7) | |
C5 | 0.0983 (4) | 0.5794 (3) | 0.40346 (10) | 0.0251 (6) | |
C6 | 0.2774 (5) | 0.5909 (3) | 0.37190 (11) | 0.0264 (7) | |
C8 | −0.1807 (5) | 0.5208 (3) | 0.44369 (11) | 0.0293 (7) | |
H8 | −0.2989 | 0.4699 | 0.4561 | 0.035* | |
C9 | −0.2672 (5) | 0.7242 (3) | 0.49399 (11) | 0.0316 (7) | |
C61 | 0.5465 (5) | 0.5280 (3) | 0.29356 (11) | 0.0296 (7) | |
H61A | 0.4725 | 0.5938 | 0.2679 | 0.036* | |
H61B | 0.6632 | 0.5752 | 0.3174 | 0.036* | |
C62 | 0.6521 (5) | 0.4179 (3) | 0.26328 (10) | 0.0265 (7) | |
C91 | −0.2175 (5) | 0.8699 (3) | 0.50110 (11) | 0.0366 (8) | |
H91A | −0.2266 | 0.9134 | 0.4658 | 0.055* | |
H91B | −0.0662 | 0.8814 | 0.5195 | 0.055* | |
H91C | −0.3271 | 0.9106 | 0.5226 | 0.055* | |
C631 | 0.8133 (4) | 0.4560 (3) | 0.22523 (10) | 0.0257 (6) | |
C632 | 0.9745 (5) | 0.3617 (3) | 0.21303 (10) | 0.0279 (7) | |
H632 | 0.9736 | 0.2748 | 0.2285 | 0.033* | |
C633 | 1.1329 (5) | 0.3927 (3) | 0.17933 (10) | 0.0278 (7) | |
H633 | 1.2425 | 0.3284 | 0.1719 | 0.033* | |
C634 | 1.1318 (5) | 0.5197 (3) | 0.15592 (11) | 0.0279 (7) | |
C635 | 0.9733 (4) | 0.6143 (3) | 0.16630 (10) | 0.0276 (7) | |
H635 | 0.9713 | 0.6998 | 0.1496 | 0.033* | |
C636 | 0.8169 (4) | 0.5822 (3) | 0.20161 (10) | 0.0264 (7) | |
H636 | 0.7105 | 0.6477 | 0.2098 | 0.032* | |
C637 | 1.3246 (5) | 0.6732 (3) | 0.10294 (12) | 0.0362 (8) | |
H63A | 1.4617 | 0.6770 | 0.0848 | 0.054* | |
H63B | 1.3370 | 0.7360 | 0.1332 | 0.054* | |
H63C | 1.1955 | 0.6977 | 0.0775 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S6 | 0.0341 (4) | 0.0194 (4) | 0.0394 (4) | −0.0023 (3) | 0.0176 (3) | −0.0022 (3) |
O6 | 0.0380 (12) | 0.0199 (12) | 0.0388 (11) | −0.0023 (9) | 0.0149 (10) | 0.0002 (9) |
O9 | 0.0413 (12) | 0.0305 (13) | 0.0479 (13) | −0.0035 (10) | 0.0236 (11) | −0.0003 (10) |
O64 | 0.0377 (12) | 0.0206 (12) | 0.0448 (12) | 0.0004 (9) | 0.0228 (10) | 0.0014 (9) |
N1 | 0.0290 (13) | 0.0206 (14) | 0.0340 (13) | −0.0009 (11) | 0.0105 (11) | 0.0005 (11) |
N3 | 0.0297 (13) | 0.0230 (14) | 0.0333 (13) | −0.0040 (11) | 0.0107 (11) | −0.0009 (10) |
N7 | 0.0326 (14) | 0.0206 (14) | 0.0372 (13) | −0.0017 (11) | 0.0128 (12) | 0.0014 (11) |
N9 | 0.0278 (13) | 0.0205 (14) | 0.0340 (13) | 0.0006 (10) | 0.0119 (11) | 0.0012 (11) |
C2 | 0.0292 (16) | 0.0226 (17) | 0.0352 (16) | −0.0051 (13) | 0.0087 (14) | −0.0006 (13) |
C4 | 0.0273 (16) | 0.0251 (17) | 0.0267 (15) | −0.0001 (13) | 0.0081 (13) | 0.0030 (12) |
C5 | 0.0237 (14) | 0.0217 (17) | 0.0311 (15) | −0.0002 (12) | 0.0091 (13) | 0.0011 (12) |
C6 | 0.0293 (15) | 0.0223 (17) | 0.0286 (15) | 0.0013 (13) | 0.0068 (13) | 0.0007 (12) |
C8 | 0.0279 (15) | 0.0247 (18) | 0.0366 (16) | −0.0026 (13) | 0.0101 (14) | 0.0031 (13) |
C9 | 0.0320 (16) | 0.0287 (18) | 0.0358 (16) | 0.0032 (14) | 0.0116 (14) | 0.0017 (13) |
C61 | 0.0370 (17) | 0.0208 (17) | 0.0336 (16) | 0.0006 (13) | 0.0160 (14) | 0.0024 (12) |
C62 | 0.0305 (16) | 0.0195 (17) | 0.0296 (15) | 0.0010 (13) | 0.0030 (13) | −0.0020 (12) |
C91 | 0.0425 (18) | 0.0283 (18) | 0.0421 (17) | −0.0003 (14) | 0.0190 (16) | −0.0020 (14) |
C631 | 0.0272 (15) | 0.0210 (16) | 0.0298 (15) | −0.0028 (12) | 0.0066 (13) | −0.0049 (12) |
C632 | 0.0360 (17) | 0.0178 (16) | 0.0303 (15) | −0.0002 (13) | 0.0054 (14) | −0.0028 (12) |
C633 | 0.0303 (15) | 0.0197 (16) | 0.0344 (15) | 0.0056 (12) | 0.0083 (14) | −0.0031 (13) |
C634 | 0.0310 (16) | 0.0236 (17) | 0.0302 (15) | −0.0045 (13) | 0.0090 (13) | −0.0033 (12) |
C635 | 0.0316 (16) | 0.0188 (16) | 0.0338 (16) | −0.0006 (13) | 0.0105 (14) | 0.0011 (12) |
C636 | 0.0271 (15) | 0.0170 (16) | 0.0362 (16) | 0.0009 (12) | 0.0091 (13) | −0.0033 (12) |
C637 | 0.0448 (19) | 0.0243 (17) | 0.0430 (18) | −0.0049 (14) | 0.0218 (16) | 0.0008 (14) |
S6—C6 | 1.741 (3) | C61—C62 | 1.510 (4) |
S6—C61 | 1.807 (3) | C61—H61A | 0.9900 |
O6—C62 | 1.224 (3) | C61—H61B | 0.9900 |
O9—C9 | 1.206 (3) | C62—C631 | 1.474 (3) |
O64—C634 | 1.368 (3) | C91—H91A | 0.9800 |
O64—C637 | 1.428 (3) | C91—H91B | 0.9800 |
N1—C6 | 1.340 (3) | C91—H91C | 0.9800 |
N1—C2 | 1.345 (3) | C631—C636 | 1.393 (4) |
N3—C2 | 1.336 (3) | C631—C632 | 1.404 (4) |
N3—C4 | 1.339 (3) | C632—C633 | 1.368 (4) |
N7—C8 | 1.299 (3) | C632—H632 | 0.9500 |
N7—C5 | 1.395 (3) | C633—C634 | 1.395 (4) |
N9—C8 | 1.394 (3) | C633—H633 | 0.9500 |
N9—C4 | 1.396 (3) | C634—C635 | 1.383 (4) |
N9—C9 | 1.422 (3) | C635—C636 | 1.389 (3) |
C2—H2 | 0.9500 | C635—H635 | 0.9500 |
C4—C5 | 1.379 (4) | C636—H636 | 0.9500 |
C5—C6 | 1.401 (4) | C637—H63A | 0.9800 |
C8—H8 | 0.9500 | C637—H63B | 0.9800 |
C9—C91 | 1.491 (4) | C637—H63C | 0.9800 |
C6—S6—C61 | 100.88 (12) | O6—C62—C61 | 120.0 (2) |
C634—O64—C637 | 118.2 (2) | C631—C62—C61 | 118.2 (2) |
C6—N1—C2 | 117.4 (2) | C9—C91—H91A | 109.5 |
C2—N3—C4 | 111.0 (2) | C9—C91—H91B | 109.5 |
C8—N7—C5 | 103.8 (2) | H91A—C91—H91B | 109.5 |
C8—N9—C4 | 105.1 (2) | C9—C91—H91C | 109.5 |
C8—N9—C9 | 122.7 (2) | H91A—C91—H91C | 109.5 |
C4—N9—C9 | 132.1 (2) | H91B—C91—H91C | 109.5 |
N3—C2—N1 | 129.3 (3) | C636—C631—C632 | 118.2 (2) |
N3—C2—H2 | 115.3 | C636—C631—C62 | 123.1 (2) |
N1—C2—H2 | 115.3 | C632—C631—C62 | 118.6 (2) |
N3—C4—C5 | 126.3 (2) | C633—C632—C631 | 121.3 (3) |
N3—C4—N9 | 128.6 (2) | C633—C632—H632 | 119.4 |
C5—C4—N9 | 105.2 (2) | C631—C632—H632 | 119.4 |
C4—C5—N7 | 111.7 (2) | C632—C633—C634 | 119.3 (2) |
C4—C5—C6 | 117.0 (2) | C632—C633—H633 | 120.3 |
N7—C5—C6 | 131.2 (2) | C634—C633—H633 | 120.3 |
N1—C6—C5 | 119.0 (2) | O64—C634—C635 | 124.0 (2) |
N1—C6—S6 | 122.46 (19) | O64—C634—C633 | 115.0 (2) |
C5—C6—S6 | 118.6 (2) | C635—C634—C633 | 121.0 (2) |
N7—C8—N9 | 114.2 (2) | C634—C635—C636 | 118.9 (3) |
N7—C8—H8 | 122.9 | C634—C635—H635 | 120.5 |
N9—C8—H8 | 122.9 | C636—C635—H635 | 120.5 |
O9—C9—N9 | 118.1 (3) | C635—C636—C631 | 121.2 (2) |
O9—C9—C91 | 125.4 (2) | C635—C636—H636 | 119.4 |
N9—C9—C91 | 116.5 (2) | C631—C636—H636 | 119.4 |
C62—C61—S6 | 108.70 (19) | O64—C637—H63A | 109.5 |
C62—C61—H61A | 109.9 | O64—C637—H63B | 109.5 |
S6—C61—H61A | 109.9 | H63A—C637—H63B | 109.5 |
C62—C61—H61B | 109.9 | O64—C637—H63C | 109.5 |
S6—C61—H61B | 109.9 | H63A—C637—H63C | 109.5 |
H61A—C61—H61B | 108.3 | H63B—C637—H63C | 109.5 |
O6—C62—C631 | 121.7 (2) | ||
C4—N3—C2—N1 | −1.2 (4) | C9—N9—C8—N7 | 176.4 (2) |
C6—N1—C2—N3 | 1.4 (4) | C8—N9—C9—O9 | 7.5 (4) |
C2—N3—C4—C5 | 0.7 (4) | C4—N9—C9—O9 | −176.6 (3) |
C2—N3—C4—N9 | −179.0 (3) | C8—N9—C9—C91 | −171.1 (3) |
C8—N9—C4—N3 | 179.8 (3) | C4—N9—C9—C91 | 4.8 (4) |
C9—N9—C4—N3 | 3.4 (5) | C6—S6—C61—C62 | 170.8 (2) |
C8—N9—C4—C5 | 0.1 (3) | S6—C61—C62—O6 | −7.7 (3) |
C9—N9—C4—C5 | −176.3 (3) | S6—C61—C62—C631 | 175.8 (2) |
N3—C4—C5—N7 | −179.5 (3) | O6—C62—C631—C636 | 160.4 (3) |
N9—C4—C5—N7 | 0.2 (3) | C61—C62—C631—C636 | −23.1 (4) |
N3—C4—C5—C6 | −0.4 (4) | O6—C62—C631—C632 | −21.1 (4) |
N9—C4—C5—C6 | 179.3 (2) | C61—C62—C631—C632 | 155.4 (3) |
C8—N7—C5—C4 | −0.5 (3) | C636—C631—C632—C633 | 0.7 (4) |
C8—N7—C5—C6 | −179.4 (3) | C62—C631—C632—C633 | −177.9 (3) |
C2—N1—C6—C5 | −0.9 (4) | C631—C632—C633—C634 | −1.1 (4) |
C2—N1—C6—S6 | 178.9 (2) | C637—O64—C634—C635 | 9.6 (4) |
C4—C5—C6—N1 | 0.5 (4) | C637—O64—C634—C633 | −171.3 (2) |
N7—C5—C6—N1 | 179.4 (3) | C632—C633—C634—O64 | −179.2 (2) |
C4—C5—C6—S6 | −179.3 (2) | C632—C633—C634—C635 | 0.0 (4) |
N7—C5—C6—S6 | −0.4 (4) | O64—C634—C635—C636 | −179.4 (2) |
C61—S6—C6—N1 | −8.5 (3) | C633—C634—C635—C636 | 1.5 (4) |
C61—S6—C6—C5 | 171.3 (2) | C634—C635—C636—C631 | −1.9 (4) |
C5—N7—C8—N9 | 0.6 (3) | C632—C631—C636—C635 | 0.9 (4) |
C4—N9—C8—N7 | −0.5 (3) | C62—C631—C636—C635 | 179.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O64i | 0.95 | 2.48 | 3.375 (3) | 157 |
C8—H8···O9ii | 0.95 | 2.37 | 3.319 (3) | 178 |
C61—H61A···O6iii | 0.99 | 2.33 | 3.269 (3) | 159 |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x−1, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2. |
C15H11ClN4O2S | F(000) = 712 |
Mr = 346.79 | Dx = 1.603 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
a = 5.9900 (4) Å | Cell parameters from 16488 reflections |
b = 9.9169 (7) Å | θ = 2.5–27.5° |
c = 24.3238 (17) Å | µ = 0.43 mm−1 |
β = 96.072 (2)° | T = 100 K |
V = 1436.78 (17) Å3 | Plate, yellow |
Z = 4 | 0.13 × 0.06 × 0.01 mm |
Rigaku AFC12 (Right) diffractometer | 3291 independent reflections |
Radiation source: Rotating Anode | 2677 reflections with I > 2σ(I) |
Detector resolution: 28.5714 pixels mm-1 | Rint = 0.050 |
profile data from ω–scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan CrystalClear-SM Expert (Rigaku, 20112) | h = −7→7 |
Tmin = 0.809, Tmax = 1.000 | k = −12→12 |
18353 measured reflections | l = −31→31 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0466P)2 + 0.5802P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
3291 reflections | Δρmax = 0.34 e Å−3 |
209 parameters | Δρmin = −0.22 e Å−3 |
C15H11ClN4O2S | V = 1436.78 (17) Å3 |
Mr = 346.79 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.9900 (4) Å | µ = 0.43 mm−1 |
b = 9.9169 (7) Å | T = 100 K |
c = 24.3238 (17) Å | 0.13 × 0.06 × 0.01 mm |
β = 96.072 (2)° |
Rigaku AFC12 (Right) diffractometer | 3291 independent reflections |
Absorption correction: multi-scan CrystalClear-SM Expert (Rigaku, 20112) | 2677 reflections with I > 2σ(I) |
Tmin = 0.809, Tmax = 1.000 | Rint = 0.050 |
18353 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.34 e Å−3 |
3291 reflections | Δρmin = −0.22 e Å−3 |
209 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl64 | 1.32087 (7) | 0.64277 (5) | 0.10411 (2) | 0.02661 (13) | |
S6 | 0.38690 (7) | 0.47381 (4) | 0.33773 (2) | 0.02313 (12) | |
O6 | 0.6478 (2) | 0.33342 (12) | 0.26796 (5) | 0.0267 (3) | |
O9 | −0.4321 (2) | 0.65965 (14) | 0.51215 (6) | 0.0325 (3) | |
N1 | 0.3921 (2) | 0.73219 (15) | 0.37483 (6) | 0.0219 (3) | |
N3 | 0.1372 (2) | 0.82388 (15) | 0.43621 (6) | 0.0227 (3) | |
N7 | −0.0233 (2) | 0.47859 (16) | 0.41129 (6) | 0.0242 (3) | |
N9 | −0.1394 (2) | 0.65498 (15) | 0.46015 (6) | 0.0223 (3) | |
C2 | 0.3079 (3) | 0.82958 (18) | 0.40503 (7) | 0.0235 (4) | |
H2 | 0.3800 | 0.9148 | 0.4041 | 0.028* | |
C4 | 0.0447 (3) | 0.70149 (19) | 0.43464 (7) | 0.0210 (3) | |
C5 | 0.1118 (3) | 0.59112 (18) | 0.40522 (7) | 0.0209 (4) | |
C6 | 0.2939 (3) | 0.61023 (18) | 0.37446 (7) | 0.0209 (4) | |
C8 | −0.1682 (3) | 0.52134 (18) | 0.44384 (7) | 0.0233 (4) | |
H8 | −0.2836 | 0.4657 | 0.4554 | 0.028* | |
C9 | −0.2805 (3) | 0.72219 (19) | 0.49567 (7) | 0.0247 (4) | |
C61 | 0.5765 (3) | 0.55799 (18) | 0.29613 (7) | 0.0231 (4) | |
H61A | 0.4932 | 0.6245 | 0.2714 | 0.028* | |
H61B | 0.6936 | 0.6065 | 0.3202 | 0.028* | |
C62 | 0.6837 (3) | 0.45309 (18) | 0.26215 (7) | 0.0215 (4) | |
C91 | −0.2263 (3) | 0.8664 (2) | 0.50911 (8) | 0.0309 (4) | |
H91A | −0.2262 | 0.9181 | 0.4748 | 0.046* | |
H91B | −0.0778 | 0.8721 | 0.5302 | 0.046* | |
H91C | −0.3393 | 0.9036 | 0.5312 | 0.046* | |
C631 | 0.8399 (3) | 0.50213 (18) | 0.22261 (7) | 0.0209 (4) | |
C632 | 1.0125 (3) | 0.41672 (18) | 0.20934 (7) | 0.0235 (4) | |
H632 | 1.0258 | 0.3290 | 0.2250 | 0.028* | |
C633 | 1.1644 (3) | 0.45870 (19) | 0.17350 (7) | 0.0238 (4) | |
H633 | 1.2840 | 0.4018 | 0.1653 | 0.029* | |
C634 | 1.1368 (3) | 0.58612 (18) | 0.15003 (7) | 0.0215 (4) | |
C635 | 0.9650 (3) | 0.67191 (18) | 0.16161 (7) | 0.0225 (4) | |
H635 | 0.9483 | 0.7580 | 0.1445 | 0.027* | |
C636 | 0.8181 (3) | 0.63008 (18) | 0.19851 (7) | 0.0214 (4) | |
H636 | 0.7018 | 0.6887 | 0.2075 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl64 | 0.0226 (2) | 0.0260 (2) | 0.0333 (2) | 0.00033 (17) | 0.01226 (17) | −0.00087 (18) |
S6 | 0.0242 (2) | 0.0180 (2) | 0.0288 (2) | −0.00324 (17) | 0.01066 (17) | −0.00245 (17) |
O6 | 0.0289 (7) | 0.0185 (7) | 0.0338 (7) | −0.0011 (5) | 0.0085 (5) | 0.0000 (5) |
O9 | 0.0269 (7) | 0.0309 (8) | 0.0423 (8) | −0.0021 (6) | 0.0161 (6) | 0.0031 (6) |
N1 | 0.0208 (7) | 0.0204 (8) | 0.0250 (8) | −0.0025 (6) | 0.0051 (6) | −0.0009 (6) |
N3 | 0.0225 (7) | 0.0200 (8) | 0.0264 (8) | −0.0019 (6) | 0.0061 (6) | −0.0013 (6) |
N7 | 0.0215 (7) | 0.0220 (8) | 0.0300 (8) | −0.0045 (6) | 0.0064 (6) | 0.0005 (6) |
N9 | 0.0189 (7) | 0.0221 (8) | 0.0269 (8) | −0.0017 (6) | 0.0065 (6) | 0.0017 (6) |
C2 | 0.0222 (8) | 0.0211 (9) | 0.0279 (9) | −0.0047 (7) | 0.0062 (7) | −0.0018 (7) |
C4 | 0.0167 (8) | 0.0253 (9) | 0.0215 (8) | 0.0010 (7) | 0.0043 (6) | 0.0017 (7) |
C5 | 0.0190 (8) | 0.0202 (9) | 0.0240 (9) | −0.0014 (7) | 0.0039 (7) | 0.0006 (7) |
C6 | 0.0183 (8) | 0.0220 (9) | 0.0227 (8) | 0.0001 (7) | 0.0042 (6) | 0.0003 (7) |
C8 | 0.0190 (8) | 0.0238 (9) | 0.0277 (9) | −0.0027 (7) | 0.0046 (7) | 0.0032 (7) |
C9 | 0.0204 (8) | 0.0272 (10) | 0.0273 (9) | 0.0006 (7) | 0.0063 (7) | 0.0018 (7) |
C61 | 0.0255 (9) | 0.0184 (9) | 0.0270 (9) | −0.0021 (7) | 0.0103 (7) | −0.0003 (7) |
C62 | 0.0199 (8) | 0.0215 (9) | 0.0232 (8) | 0.0017 (7) | 0.0025 (6) | −0.0008 (7) |
C91 | 0.0274 (9) | 0.0307 (11) | 0.0366 (11) | −0.0025 (8) | 0.0134 (8) | −0.0072 (8) |
C631 | 0.0193 (8) | 0.0202 (9) | 0.0235 (9) | −0.0001 (7) | 0.0045 (7) | −0.0025 (7) |
C632 | 0.0252 (9) | 0.0182 (9) | 0.0275 (9) | 0.0031 (7) | 0.0048 (7) | 0.0009 (7) |
C633 | 0.0202 (8) | 0.0248 (10) | 0.0270 (9) | 0.0051 (7) | 0.0050 (7) | −0.0022 (7) |
C634 | 0.0187 (8) | 0.0225 (9) | 0.0239 (9) | −0.0017 (7) | 0.0058 (7) | −0.0032 (7) |
C635 | 0.0232 (8) | 0.0173 (9) | 0.0279 (9) | 0.0008 (7) | 0.0062 (7) | −0.0003 (7) |
C636 | 0.0200 (8) | 0.0181 (9) | 0.0270 (9) | 0.0018 (7) | 0.0063 (7) | −0.0030 (7) |
Cl64—C634 | 1.7433 (17) | C9—C91 | 1.495 (3) |
S6—C6 | 1.7446 (18) | C61—C62 | 1.513 (2) |
S6—C61 | 1.8038 (17) | C61—H61A | 0.9900 |
O6—C62 | 1.217 (2) | C61—H61B | 0.9900 |
O9—C9 | 1.203 (2) | C62—C631 | 1.493 (2) |
N1—C2 | 1.344 (2) | C91—H91A | 0.9800 |
N1—C6 | 1.344 (2) | C91—H91B | 0.9800 |
N3—C4 | 1.333 (2) | C91—H91C | 0.9800 |
N3—C2 | 1.337 (2) | C631—C636 | 1.398 (2) |
N7—C8 | 1.306 (2) | C631—C632 | 1.400 (2) |
N7—C5 | 1.395 (2) | C632—C633 | 1.389 (2) |
N9—C8 | 1.389 (2) | C632—H632 | 0.9500 |
N9—C4 | 1.400 (2) | C633—C634 | 1.389 (3) |
N9—C9 | 1.435 (2) | C633—H633 | 0.9500 |
C2—H2 | 0.9500 | C634—C635 | 1.387 (2) |
C4—C5 | 1.390 (2) | C635—C636 | 1.385 (2) |
C5—C6 | 1.400 (2) | C635—H635 | 0.9500 |
C8—H8 | 0.9500 | C636—H636 | 0.9500 |
C6—S6—C61 | 100.50 (8) | S6—C61—H61B | 110.0 |
C2—N1—C6 | 117.46 (15) | H61A—C61—H61B | 108.4 |
C4—N3—C2 | 111.27 (15) | O6—C62—C631 | 121.52 (16) |
C8—N7—C5 | 103.57 (15) | O6—C62—C61 | 121.13 (16) |
C8—N9—C4 | 105.53 (14) | C631—C62—C61 | 117.33 (15) |
C8—N9—C9 | 123.49 (15) | C9—C91—H91A | 109.5 |
C4—N9—C9 | 130.97 (15) | C9—C91—H91B | 109.5 |
N3—C2—N1 | 129.31 (16) | H91A—C91—H91B | 109.5 |
N3—C2—H2 | 115.3 | C9—C91—H91C | 109.5 |
N1—C2—H2 | 115.3 | H91A—C91—H91C | 109.5 |
N3—C4—C5 | 126.14 (15) | H91B—C91—H91C | 109.5 |
N3—C4—N9 | 129.20 (16) | C636—C631—C632 | 119.40 (16) |
C5—C4—N9 | 104.65 (15) | C636—C631—C62 | 121.92 (15) |
C4—C5—N7 | 111.89 (15) | C632—C631—C62 | 118.68 (16) |
C4—C5—C6 | 116.91 (16) | C633—C632—C631 | 120.80 (17) |
N7—C5—C6 | 131.18 (16) | C633—C632—H632 | 119.6 |
N1—C6—C5 | 118.90 (16) | C631—C632—H632 | 119.6 |
N1—C6—S6 | 122.55 (12) | C632—C633—C634 | 118.25 (16) |
C5—C6—S6 | 118.54 (13) | C632—C633—H633 | 120.9 |
N7—C8—N9 | 114.35 (15) | C634—C633—H633 | 120.9 |
N7—C8—H8 | 122.8 | C635—C634—C633 | 122.19 (16) |
N9—C8—H8 | 122.8 | C635—C634—Cl64 | 117.76 (14) |
O9—C9—N9 | 118.34 (17) | C633—C634—Cl64 | 120.05 (13) |
O9—C9—C91 | 125.05 (17) | C636—C635—C634 | 118.94 (16) |
N9—C9—C91 | 116.61 (15) | C636—C635—H635 | 120.5 |
C62—C61—S6 | 108.47 (12) | C634—C635—H635 | 120.5 |
C62—C61—H61A | 110.0 | C635—C636—C631 | 120.38 (16) |
S6—C61—H61A | 110.0 | C635—C636—H636 | 119.8 |
C62—C61—H61B | 110.0 | C631—C636—H636 | 119.8 |
C4—N3—C2—N1 | −0.7 (3) | C4—N9—C8—N7 | 0.2 (2) |
C6—N1—C2—N3 | 0.7 (3) | C9—N9—C8—N7 | 179.77 (16) |
C2—N3—C4—C5 | 0.2 (3) | C8—N9—C9—O9 | −0.1 (3) |
C2—N3—C4—N9 | −178.24 (17) | C4—N9—C9—O9 | 179.26 (18) |
C8—N9—C4—N3 | 178.49 (18) | C8—N9—C9—C91 | −179.93 (17) |
C9—N9—C4—N3 | −1.0 (3) | C4—N9—C9—C91 | −0.5 (3) |
C8—N9—C4—C5 | −0.24 (18) | C6—S6—C61—C62 | 177.77 (12) |
C9—N9—C4—C5 | −179.73 (17) | S6—C61—C62—O6 | −4.5 (2) |
N3—C4—C5—N7 | −178.60 (16) | S6—C61—C62—C631 | 177.32 (12) |
N9—C4—C5—N7 | 0.2 (2) | O6—C62—C631—C636 | 153.51 (18) |
N3—C4—C5—C6 | 0.2 (3) | C61—C62—C631—C636 | −28.3 (2) |
N9—C4—C5—C6 | 178.95 (15) | O6—C62—C631—C632 | −26.3 (3) |
C8—N7—C5—C4 | −0.1 (2) | C61—C62—C631—C632 | 151.92 (17) |
C8—N7—C5—C6 | −178.58 (19) | C636—C631—C632—C633 | 1.3 (3) |
C2—N1—C6—C5 | −0.1 (2) | C62—C631—C632—C633 | −178.87 (16) |
C2—N1—C6—S6 | −179.32 (13) | C631—C632—C633—C634 | −1.7 (3) |
C4—C5—C6—N1 | −0.2 (2) | C632—C633—C634—C635 | 0.5 (3) |
N7—C5—C6—N1 | 178.25 (17) | C632—C633—C634—Cl64 | −179.20 (13) |
C4—C5—C6—S6 | 179.00 (13) | C633—C634—C635—C636 | 1.1 (3) |
N7—C5—C6—S6 | −2.5 (3) | Cl64—C634—C635—C636 | −179.18 (13) |
C61—S6—C6—N1 | −11.73 (17) | C634—C635—C636—C631 | −1.5 (3) |
C61—S6—C6—C5 | 169.08 (14) | C632—C631—C636—C635 | 0.3 (3) |
C5—N7—C8—N9 | −0.1 (2) | C62—C631—C636—C635 | −179.47 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O9i | 0.95 | 2.31 | 3.262 (2) | 176 |
C61—H61A···O6ii | 0.99 | 2.40 | 3.354 (2) | 162 |
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+1/2. |
C15H11BrN4O2S | F(000) = 784 |
Mr = 391.25 | Dx = 1.758 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
a = 6.0705 (4) Å | Cell parameters from 18109 reflections |
b = 10.0668 (7) Å | θ = 2.5–27.5° |
c = 24.3492 (17) Å | µ = 2.94 mm−1 |
β = 96.580 (2)° | T = 100 K |
V = 1478.19 (18) Å3 | Plate, colourless |
Z = 4 | 0.15 × 0.10 × 0.02 mm |
Rigaku AFC12 (Right) diffractometer | 3346 independent reflections |
Radiation source: Rotating Anode | 2944 reflections with I > 2σ(I) |
Detector resolution: 28.5714 pixels mm-1 | Rint = 0.064 |
profile data from ω–scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan CrystalClear-SM Expert (Rigaku, 20112) | h = −7→7 |
Tmin = 0.658, Tmax = 1.000 | k = −12→13 |
18171 measured reflections | l = −31→31 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.1178P)2 + 0.358P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
3346 reflections | Δρmax = 2.91 e Å−3 |
209 parameters | Δρmin = −0.92 e Å−3 |
C15H11BrN4O2S | V = 1478.19 (18) Å3 |
Mr = 391.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.0705 (4) Å | µ = 2.94 mm−1 |
b = 10.0668 (7) Å | T = 100 K |
c = 24.3492 (17) Å | 0.15 × 0.10 × 0.02 mm |
β = 96.580 (2)° |
Rigaku AFC12 (Right) diffractometer | 3346 independent reflections |
Absorption correction: multi-scan CrystalClear-SM Expert (Rigaku, 20112) | 2944 reflections with I > 2σ(I) |
Tmin = 0.658, Tmax = 1.000 | Rint = 0.064 |
18171 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.06 | Δρmax = 2.91 e Å−3 |
3346 reflections | Δρmin = −0.92 e Å−3 |
209 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br64 | 1.32442 (5) | 0.33869 (3) | 0.10086 (2) | 0.02971 (16) | |
S6 | 0.38570 (14) | 0.51673 (7) | 0.33803 (3) | 0.0278 (2) | |
O6 | 0.6441 (5) | 0.6537 (2) | 0.26801 (11) | 0.0318 (5) | |
O9 | −0.4299 (5) | 0.3392 (2) | 0.51161 (11) | 0.0357 (6) | |
N1 | 0.3870 (5) | 0.2608 (3) | 0.37506 (10) | 0.0267 (5) | |
N3 | 0.1320 (5) | 0.1721 (2) | 0.43630 (12) | 0.0279 (6) | |
N7 | −0.0199 (5) | 0.5157 (3) | 0.41162 (11) | 0.0274 (5) | |
N9 | −0.1388 (5) | 0.3411 (2) | 0.46032 (12) | 0.0263 (6) | |
C2 | 0.3003 (6) | 0.1653 (3) | 0.40499 (14) | 0.0290 (7) | |
H2 | 0.3683 | 0.0806 | 0.4038 | 0.035* | |
C4 | 0.0420 (5) | 0.2942 (3) | 0.43479 (12) | 0.0260 (6) | |
C5 | 0.1121 (5) | 0.4027 (3) | 0.40513 (12) | 0.0262 (6) | |
C6 | 0.2904 (5) | 0.3823 (3) | 0.37469 (12) | 0.0255 (6) | |
C8 | −0.1649 (5) | 0.4742 (3) | 0.44429 (12) | 0.0274 (6) | |
H8 | −0.2771 | 0.5298 | 0.4559 | 0.033* | |
C9 | −0.2823 (5) | 0.2762 (3) | 0.49460 (13) | 0.0279 (6) | |
C61 | 0.5714 (5) | 0.4314 (3) | 0.29665 (13) | 0.0278 (6) | |
H61A | 0.6861 | 0.3827 | 0.3209 | 0.033* | |
H61B | 0.4876 | 0.3666 | 0.2718 | 0.033* | |
C62 | 0.6802 (5) | 0.5351 (3) | 0.26272 (12) | 0.0267 (6) | |
C91 | −0.2352 (6) | 0.1307 (4) | 0.50629 (16) | 0.0346 (7) | |
H91A | −0.2341 | 0.0827 | 0.4713 | 0.052* | |
H91B | −0.3506 | 0.0937 | 0.5268 | 0.052* | |
H91C | −0.0904 | 0.1214 | 0.5283 | 0.052* | |
C631 | 0.8358 (5) | 0.4855 (3) | 0.22393 (12) | 0.0248 (6) | |
C632 | 1.0055 (6) | 0.5701 (3) | 0.20986 (13) | 0.0292 (6) | |
H632 | 1.0178 | 0.6572 | 0.2250 | 0.035* | |
C633 | 1.1556 (5) | 0.5285 (3) | 0.17420 (13) | 0.0282 (6) | |
H633 | 1.2725 | 0.5850 | 0.1657 | 0.034* | |
C634 | 1.1296 (5) | 0.4012 (3) | 0.15118 (12) | 0.0262 (6) | |
C635 | 0.9596 (6) | 0.3157 (3) | 0.16372 (14) | 0.0291 (6) | |
H635 | 0.9435 | 0.2301 | 0.1473 | 0.035* | |
C636 | 0.8144 (6) | 0.3585 (3) | 0.20067 (14) | 0.0273 (6) | |
H636 | 0.7005 | 0.3009 | 0.2100 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br64 | 0.0279 (2) | 0.0250 (2) | 0.0387 (2) | 0.00019 (11) | 0.01488 (15) | 0.00074 (10) |
S6 | 0.0299 (4) | 0.0199 (4) | 0.0361 (4) | 0.0021 (3) | 0.0142 (3) | 0.0016 (3) |
O6 | 0.0370 (13) | 0.0205 (12) | 0.0399 (12) | 0.0015 (9) | 0.0127 (10) | −0.0010 (8) |
O9 | 0.0334 (14) | 0.0301 (14) | 0.0469 (14) | 0.0016 (9) | 0.0193 (11) | −0.0011 (9) |
N1 | 0.0255 (13) | 0.0225 (13) | 0.0335 (12) | 0.0028 (10) | 0.0101 (10) | 0.0010 (10) |
N3 | 0.0316 (15) | 0.0206 (13) | 0.0328 (13) | 0.0045 (10) | 0.0095 (11) | 0.0032 (9) |
N7 | 0.0258 (13) | 0.0214 (13) | 0.0366 (13) | 0.0036 (10) | 0.0104 (10) | −0.0008 (10) |
N9 | 0.0266 (14) | 0.0206 (14) | 0.0332 (13) | 0.0012 (9) | 0.0096 (11) | −0.0011 (9) |
C2 | 0.0296 (16) | 0.0222 (16) | 0.0365 (16) | 0.0043 (11) | 0.0087 (13) | 0.0015 (11) |
C4 | 0.0260 (15) | 0.0258 (16) | 0.0277 (13) | −0.0002 (12) | 0.0091 (11) | −0.0006 (12) |
C5 | 0.0267 (16) | 0.0202 (15) | 0.0325 (14) | 0.0035 (11) | 0.0065 (11) | 0.0008 (11) |
C6 | 0.0249 (15) | 0.0209 (14) | 0.0316 (14) | 0.0006 (11) | 0.0070 (11) | 0.0007 (12) |
C8 | 0.0284 (16) | 0.0214 (15) | 0.0332 (14) | 0.0025 (11) | 0.0070 (11) | −0.0002 (11) |
C9 | 0.0255 (15) | 0.0255 (16) | 0.0342 (14) | −0.0002 (12) | 0.0097 (11) | −0.0009 (12) |
C61 | 0.0298 (16) | 0.0202 (15) | 0.0358 (14) | 0.0003 (11) | 0.0143 (12) | −0.0001 (12) |
C62 | 0.0269 (16) | 0.0230 (15) | 0.0312 (14) | −0.0026 (11) | 0.0081 (11) | −0.0012 (11) |
C91 | 0.0343 (18) | 0.0275 (16) | 0.0448 (18) | 0.0033 (14) | 0.0162 (14) | 0.0072 (14) |
C631 | 0.0251 (15) | 0.0218 (15) | 0.0287 (13) | 0.0013 (11) | 0.0079 (11) | −0.0003 (11) |
C632 | 0.0317 (16) | 0.0207 (15) | 0.0364 (15) | −0.0020 (12) | 0.0098 (12) | −0.0007 (12) |
C633 | 0.0272 (16) | 0.0246 (16) | 0.0339 (14) | −0.0036 (12) | 0.0086 (11) | 0.0017 (12) |
C634 | 0.0246 (15) | 0.0232 (15) | 0.0321 (14) | 0.0001 (11) | 0.0085 (11) | 0.0015 (11) |
C635 | 0.0318 (17) | 0.0199 (14) | 0.0376 (15) | −0.0025 (12) | 0.0127 (13) | −0.0016 (12) |
C636 | 0.0288 (16) | 0.0187 (14) | 0.0360 (15) | −0.0017 (11) | 0.0098 (13) | 0.0011 (11) |
Br64—C634 | 1.905 (3) | C9—C91 | 1.513 (5) |
S6—C6 | 1.755 (3) | C61—C62 | 1.528 (4) |
S6—C61 | 1.812 (3) | C61—H61A | 0.9900 |
O6—C62 | 1.224 (4) | C61—H61B | 0.9900 |
O9—C9 | 1.209 (4) | C62—C631 | 1.496 (4) |
N1—C2 | 1.349 (4) | C91—H91A | 0.9800 |
N1—C6 | 1.356 (4) | C91—H91B | 0.9800 |
N3—C4 | 1.344 (4) | C91—H91C | 0.9800 |
N3—C2 | 1.345 (5) | C631—C636 | 1.398 (4) |
N7—C8 | 1.320 (4) | C631—C632 | 1.409 (5) |
N7—C5 | 1.411 (4) | C632—C633 | 1.393 (5) |
N9—C8 | 1.399 (4) | C632—H632 | 0.9500 |
N9—C4 | 1.404 (4) | C633—C634 | 1.400 (4) |
N9—C9 | 1.431 (4) | C633—H633 | 0.9500 |
C2—H2 | 0.9500 | C634—C635 | 1.404 (4) |
C4—C5 | 1.402 (4) | C635—C636 | 1.398 (5) |
C5—C6 | 1.395 (4) | C635—H635 | 0.9500 |
C8—H8 | 0.9500 | C636—H636 | 0.9500 |
C6—S6—C61 | 100.33 (15) | S6—C61—H61B | 110.1 |
C2—N1—C6 | 116.8 (3) | H61A—C61—H61B | 108.4 |
C4—N3—C2 | 111.3 (3) | O6—C62—C631 | 121.7 (3) |
C8—N7—C5 | 103.8 (3) | O6—C62—C61 | 121.1 (3) |
C8—N9—C4 | 105.5 (3) | C631—C62—C61 | 117.2 (3) |
C8—N9—C9 | 122.9 (3) | C9—C91—H91A | 109.5 |
C4—N9—C9 | 131.6 (3) | C9—C91—H91B | 109.5 |
N3—C2—N1 | 129.7 (3) | H91A—C91—H91B | 109.5 |
N3—C2—H2 | 115.1 | C9—C91—H91C | 109.5 |
N1—C2—H2 | 115.1 | H91A—C91—H91C | 109.5 |
N3—C4—C5 | 125.4 (3) | H91B—C91—H91C | 109.5 |
N3—C4—N9 | 129.2 (3) | C636—C631—C632 | 119.4 (3) |
C5—C4—N9 | 105.4 (3) | C636—C631—C62 | 121.6 (3) |
C6—C5—C4 | 117.3 (3) | C632—C631—C62 | 118.9 (3) |
C6—C5—N7 | 131.5 (3) | C633—C632—C631 | 121.2 (3) |
C4—C5—N7 | 111.1 (3) | C633—C632—H632 | 119.4 |
N1—C6—C5 | 119.4 (3) | C631—C632—H632 | 119.4 |
N1—C6—S6 | 122.1 (2) | C632—C633—C634 | 118.2 (3) |
C5—C6—S6 | 118.5 (2) | C632—C633—H633 | 120.9 |
N7—C8—N9 | 114.2 (3) | C634—C633—H633 | 120.9 |
N7—C8—H8 | 122.9 | C633—C634—C635 | 121.7 (3) |
N9—C8—H8 | 122.9 | C633—C634—Br64 | 120.7 (2) |
O9—C9—N9 | 119.0 (3) | C635—C634—Br64 | 117.6 (2) |
O9—C9—C91 | 125.1 (3) | C636—C635—C634 | 119.0 (3) |
N9—C9—C91 | 115.9 (3) | C636—C635—H635 | 120.5 |
C62—C61—S6 | 108.2 (2) | C634—C635—H635 | 120.5 |
C62—C61—H61A | 110.1 | C635—C636—C631 | 120.4 (3) |
S6—C61—H61A | 110.1 | C635—C636—H636 | 119.8 |
C62—C61—H61B | 110.1 | C631—C636—H636 | 119.8 |
C4—N3—C2—N1 | 1.4 (5) | C4—N9—C8—N7 | −0.1 (4) |
C6—N1—C2—N3 | −1.6 (5) | C9—N9—C8—N7 | −178.5 (3) |
C2—N3—C4—C5 | −0.5 (5) | C8—N9—C9—O9 | −1.6 (5) |
C2—N3—C4—N9 | 178.1 (3) | C4—N9—C9—O9 | −179.6 (3) |
C8—N9—C4—N3 | −178.8 (3) | C8—N9—C9—C91 | 177.9 (3) |
C9—N9—C4—N3 | −0.6 (6) | C4—N9—C9—C91 | 0.0 (5) |
C8—N9—C4—C5 | 0.0 (3) | C6—S6—C61—C62 | −177.8 (2) |
C9—N9—C4—C5 | 178.2 (3) | S6—C61—C62—O6 | 3.2 (4) |
N3—C4—C5—C6 | −0.1 (5) | S6—C61—C62—C631 | −178.1 (2) |
N9—C4—C5—C6 | −179.0 (3) | O6—C62—C631—C636 | −153.8 (3) |
N3—C4—C5—N7 | 179.0 (3) | C61—C62—C631—C636 | 27.6 (4) |
N9—C4—C5—N7 | 0.1 (3) | O6—C62—C631—C632 | 25.1 (4) |
C8—N7—C5—C6 | 178.7 (3) | C61—C62—C631—C632 | −153.6 (3) |
C8—N7—C5—C4 | −0.2 (3) | C636—C631—C632—C633 | −1.5 (5) |
C2—N1—C6—C5 | 0.8 (4) | C62—C631—C632—C633 | 179.6 (3) |
C2—N1—C6—S6 | 179.6 (2) | C631—C632—C633—C634 | 1.9 (5) |
C4—C5—C6—N1 | −0.1 (4) | C632—C633—C634—C635 | −0.8 (5) |
N7—C5—C6—N1 | −179.0 (3) | C632—C633—C634—Br64 | 178.7 (2) |
C4—C5—C6—S6 | −178.9 (2) | C633—C634—C635—C636 | −0.8 (5) |
N7—C5—C6—S6 | 2.2 (5) | Br64—C634—C635—C636 | 179.8 (2) |
C61—S6—C6—N1 | 12.0 (3) | C634—C635—C636—C631 | 1.2 (5) |
C61—S6—C6—C5 | −169.3 (3) | C632—C631—C636—C635 | −0.1 (5) |
C5—N7—C8—N9 | 0.2 (4) | C62—C631—C636—C635 | 178.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O9i | 0.95 | 2.42 | 3.367 (4) | 177 |
C61—H61B···O6ii | 0.99 | 2.45 | 3.396 (4) | 160 |
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2. |
C14H12N4O2S | F(000) = 624 |
Mr = 300.34 | Dx = 1.487 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
a = 7.6683 (5) Å | Cell parameters from 16870 reflections |
b = 21.8004 (15) Å | θ = 2.5–27.5° |
c = 8.4131 (5) Å | µ = 0.25 mm−1 |
β = 107.507 (2)° | T = 100 K |
V = 1341.29 (15) Å3 | Block, colourless |
Z = 4 | 0.17 × 0.12 × 0.07 mm |
Rigaku AFC12 (Right) diffractometer | 3063 independent reflections |
Radiation source: Rotating Anode | 2799 reflections with I > 2σ(I) |
Detector resolution: 28.5714 pixels mm-1 | Rint = 0.060 |
profile data from ω–scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012) | h = −9→9 |
Tmin = 0.724, Tmax = 1.000 | k = −28→28 |
17441 measured reflections | l = −10→10 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.055P)2 + 0.4055P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
3063 reflections | Δρmax = 0.30 e Å−3 |
191 parameters | Δρmin = −0.37 e Å−3 |
C14H12N4O2S | V = 1341.29 (15) Å3 |
Mr = 300.34 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.6683 (5) Å | µ = 0.25 mm−1 |
b = 21.8004 (15) Å | T = 100 K |
c = 8.4131 (5) Å | 0.17 × 0.12 × 0.07 mm |
β = 107.507 (2)° |
Rigaku AFC12 (Right) diffractometer | 3063 independent reflections |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012) | 2799 reflections with I > 2σ(I) |
Tmin = 0.724, Tmax = 1.000 | Rint = 0.060 |
17441 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.30 e Å−3 |
3063 reflections | Δρmin = −0.37 e Å−3 |
191 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S6 | 0.17185 (4) | 0.41173 (2) | 0.46144 (3) | 0.02043 (11) | |
O6 | 0.42208 (12) | 0.47291 (4) | 0.71480 (12) | 0.0275 (2) | |
O63 | 0.70355 (13) | 0.67387 (4) | 0.97072 (11) | 0.0288 (2) | |
N1 | −0.06585 (14) | 0.44463 (5) | 0.16289 (13) | 0.0227 (2) | |
N3 | −0.25987 (15) | 0.37375 (5) | −0.03578 (13) | 0.0240 (2) | |
N7 | 0.01119 (14) | 0.28258 (5) | 0.30139 (13) | 0.0211 (2) | |
N9 | −0.21099 (14) | 0.26758 (5) | 0.06007 (13) | 0.0226 (2) | |
H9 | −0.2911 | 0.2481 | −0.0214 | 0.027* | |
C2 | −0.19450 (17) | 0.42912 (6) | 0.01862 (15) | 0.0247 (3) | |
H6 | −0.2451 | 0.4623 | −0.0538 | 0.030* | |
C4 | −0.17933 (16) | 0.32957 (6) | 0.07248 (15) | 0.0206 (2) | |
C5 | −0.04241 (16) | 0.33841 (5) | 0.22326 (14) | 0.0195 (2) | |
C6 | 0.01075 (15) | 0.39879 (6) | 0.26754 (14) | 0.0194 (2) | |
C8 | −0.09352 (16) | 0.24220 (6) | 0.19916 (15) | 0.0225 (3) | |
H8 | −0.0874 | 0.1993 | 0.2207 | 0.027* | |
C61 | 0.21217 (16) | 0.49315 (6) | 0.44829 (15) | 0.0213 (2) | |
H61A | 0.2602 | 0.5018 | 0.3537 | 0.026* | |
H61B | 0.0969 | 0.5163 | 0.4312 | 0.026* | |
C62 | 0.35075 (16) | 0.51187 (6) | 0.61124 (15) | 0.0207 (2) | |
C631 | 0.39980 (16) | 0.57789 (6) | 0.63995 (15) | 0.0205 (2) | |
C632 | 0.52582 (16) | 0.59345 (5) | 0.79351 (15) | 0.0208 (2) | |
H632 | 0.5744 | 0.5626 | 0.8745 | 0.025* | |
C633 | 0.57924 (17) | 0.65409 (6) | 0.82667 (16) | 0.0230 (3) | |
C634 | 0.50351 (18) | 0.69940 (6) | 0.70857 (17) | 0.0259 (3) | |
H634 | 0.5385 | 0.7410 | 0.7320 | 0.031* | |
C635 | 0.37787 (18) | 0.68404 (6) | 0.55762 (17) | 0.0265 (3) | |
H635 | 0.3264 | 0.7152 | 0.4785 | 0.032* | |
C636 | 0.32641 (16) | 0.62298 (6) | 0.52100 (16) | 0.0238 (3) | |
H636 | 0.2425 | 0.6123 | 0.4164 | 0.029* | |
C637 | 0.7840 (2) | 0.62823 (6) | 1.09270 (17) | 0.0301 (3) | |
H63A | 0.8724 | 0.6476 | 1.1886 | 0.045* | |
H63B | 0.8465 | 0.5976 | 1.0440 | 0.045* | |
H63C | 0.6882 | 0.6081 | 1.1291 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S6 | 0.02055 (17) | 0.02018 (17) | 0.01696 (16) | −0.00081 (10) | 0.00019 (11) | −0.00014 (10) |
O6 | 0.0294 (5) | 0.0212 (5) | 0.0250 (5) | −0.0002 (3) | −0.0021 (4) | 0.0020 (3) |
O63 | 0.0378 (5) | 0.0234 (5) | 0.0227 (5) | −0.0077 (4) | 0.0053 (4) | −0.0043 (4) |
N1 | 0.0231 (5) | 0.0235 (5) | 0.0196 (5) | 0.0015 (4) | 0.0036 (4) | 0.0024 (4) |
N3 | 0.0229 (5) | 0.0282 (6) | 0.0173 (5) | 0.0029 (4) | 0.0005 (4) | 0.0022 (4) |
N7 | 0.0203 (5) | 0.0220 (5) | 0.0178 (5) | 0.0011 (4) | 0.0009 (4) | 0.0009 (4) |
N9 | 0.0214 (5) | 0.0242 (5) | 0.0179 (5) | 0.0001 (4) | −0.0005 (4) | −0.0024 (4) |
C2 | 0.0250 (6) | 0.0272 (7) | 0.0185 (6) | 0.0038 (5) | 0.0016 (5) | 0.0042 (5) |
C4 | 0.0188 (5) | 0.0249 (6) | 0.0161 (5) | 0.0011 (4) | 0.0023 (4) | −0.0012 (5) |
C5 | 0.0180 (5) | 0.0233 (6) | 0.0150 (5) | 0.0015 (4) | 0.0014 (4) | 0.0006 (4) |
C6 | 0.0179 (5) | 0.0227 (6) | 0.0166 (5) | 0.0006 (4) | 0.0038 (4) | 0.0006 (4) |
C8 | 0.0224 (6) | 0.0222 (6) | 0.0199 (6) | 0.0004 (4) | 0.0019 (4) | 0.0000 (5) |
C61 | 0.0206 (5) | 0.0209 (6) | 0.0203 (6) | −0.0011 (4) | 0.0030 (5) | −0.0002 (4) |
C62 | 0.0183 (5) | 0.0225 (6) | 0.0204 (6) | 0.0000 (4) | 0.0046 (4) | −0.0003 (4) |
C631 | 0.0187 (5) | 0.0219 (6) | 0.0210 (6) | 0.0000 (4) | 0.0060 (4) | −0.0006 (4) |
C632 | 0.0229 (6) | 0.0202 (6) | 0.0195 (6) | 0.0003 (4) | 0.0065 (5) | −0.0007 (4) |
C633 | 0.0248 (6) | 0.0240 (6) | 0.0216 (6) | −0.0028 (5) | 0.0091 (5) | −0.0030 (5) |
C634 | 0.0298 (6) | 0.0184 (6) | 0.0312 (7) | −0.0018 (5) | 0.0118 (5) | −0.0006 (5) |
C635 | 0.0262 (6) | 0.0228 (6) | 0.0302 (7) | 0.0021 (5) | 0.0082 (5) | 0.0053 (5) |
C636 | 0.0208 (6) | 0.0247 (7) | 0.0241 (6) | 0.0001 (4) | 0.0042 (5) | 0.0026 (5) |
C637 | 0.0350 (7) | 0.0315 (7) | 0.0209 (6) | −0.0054 (5) | 0.0039 (5) | −0.0024 (5) |
S6—C6 | 1.7477 (12) | C61—C62 | 1.5162 (16) |
S6—C61 | 1.8109 (13) | C61—H61A | 0.9900 |
O6—C62 | 1.2219 (15) | C61—H61B | 0.9900 |
O63—C633 | 1.3669 (15) | C62—C631 | 1.4887 (17) |
O63—C637 | 1.4293 (17) | C631—C636 | 1.3949 (17) |
N1—C6 | 1.3446 (16) | C631—C632 | 1.4025 (17) |
N1—C2 | 1.3566 (16) | C632—C633 | 1.3871 (17) |
N3—C2 | 1.3342 (17) | C632—H632 | 0.9500 |
N3—C4 | 1.3416 (16) | C633—C634 | 1.3975 (18) |
N7—C8 | 1.3206 (16) | C634—C635 | 1.3846 (19) |
N7—C5 | 1.3855 (15) | C634—H634 | 0.9500 |
N9—C8 | 1.3612 (15) | C635—C636 | 1.3963 (18) |
N9—C4 | 1.3716 (16) | C635—H635 | 0.9500 |
N9—H9 | 0.8800 | C636—H636 | 0.9500 |
C2—H6 | 0.9500 | C637—H63A | 0.9800 |
C4—C5 | 1.3954 (16) | C637—H63B | 0.9800 |
C5—C6 | 1.3950 (17) | C637—H63C | 0.9800 |
C8—H8 | 0.9500 | ||
C6—S6—C61 | 100.77 (6) | H61A—C61—H61B | 108.5 |
C633—O63—C637 | 116.88 (10) | O6—C62—C631 | 121.28 (11) |
C6—N1—C2 | 117.22 (11) | O6—C62—C61 | 119.95 (11) |
C2—N3—C4 | 111.58 (11) | C631—C62—C61 | 118.75 (10) |
C8—N7—C5 | 103.95 (10) | C636—C631—C632 | 120.52 (11) |
C8—N9—C4 | 106.19 (10) | C636—C631—C62 | 122.49 (11) |
C8—N9—H9 | 126.9 | C632—C631—C62 | 116.99 (11) |
C4—N9—H9 | 126.9 | C633—C632—C631 | 119.72 (12) |
N3—C2—N1 | 129.01 (12) | C633—C632—H632 | 120.1 |
N3—C2—H6 | 115.5 | C631—C632—H632 | 120.1 |
N1—C2—H6 | 115.5 | O63—C633—C632 | 124.33 (12) |
N3—C4—N9 | 128.37 (11) | O63—C633—C634 | 115.92 (11) |
N3—C4—C5 | 125.80 (12) | C632—C633—C634 | 119.75 (12) |
N9—C4—C5 | 105.83 (10) | C635—C634—C633 | 120.46 (12) |
N7—C5—C6 | 132.92 (11) | C635—C634—H634 | 119.8 |
N7—C5—C4 | 110.17 (11) | C633—C634—H634 | 119.8 |
C6—C5—C4 | 116.90 (11) | C634—C635—C636 | 120.36 (12) |
N1—C6—C5 | 119.44 (11) | C634—C635—H635 | 119.8 |
N1—C6—S6 | 122.55 (10) | C636—C635—H635 | 119.8 |
C5—C6—S6 | 117.99 (9) | C631—C636—C635 | 119.17 (12) |
N7—C8—N9 | 113.85 (11) | C631—C636—H636 | 120.4 |
N7—C8—H8 | 123.1 | C635—C636—H636 | 120.4 |
N9—C8—H8 | 123.1 | O63—C637—H63A | 109.5 |
C62—C61—S6 | 107.14 (8) | O63—C637—H63B | 109.5 |
C62—C61—H61A | 110.3 | H63A—C637—H63B | 109.5 |
S6—C61—H61A | 110.3 | O63—C637—H63C | 109.5 |
C62—C61—H61B | 110.3 | H63A—C637—H63C | 109.5 |
S6—C61—H61B | 110.3 | H63B—C637—H63C | 109.5 |
C4—N3—C2—N1 | −0.95 (19) | C4—N9—C8—N7 | 0.34 (14) |
C6—N1—C2—N3 | 0.9 (2) | C6—S6—C61—C62 | 179.54 (8) |
C2—N3—C4—N9 | 179.68 (12) | S6—C61—C62—O6 | 5.56 (14) |
C2—N3—C4—C5 | −0.74 (18) | S6—C61—C62—C631 | −175.65 (9) |
C8—N9—C4—N3 | 178.96 (12) | O6—C62—C631—C636 | 177.18 (11) |
C8—N9—C4—C5 | −0.68 (13) | C61—C62—C631—C636 | −1.59 (17) |
C8—N7—C5—C6 | 178.02 (13) | O6—C62—C631—C632 | −2.42 (17) |
C8—N7—C5—C4 | −0.60 (13) | C61—C62—C631—C632 | 178.81 (10) |
N3—C4—C5—N7 | −178.84 (11) | C636—C631—C632—C633 | −0.64 (18) |
N9—C4—C5—N7 | 0.81 (13) | C62—C631—C632—C633 | 178.98 (11) |
N3—C4—C5—C6 | 2.29 (18) | C637—O63—C633—C632 | 0.86 (17) |
N9—C4—C5—C6 | −178.05 (10) | C637—O63—C633—C634 | −179.47 (11) |
C2—N1—C6—C5 | 0.84 (17) | C631—C632—C633—O63 | −178.68 (11) |
C2—N1—C6—S6 | −177.49 (9) | C631—C632—C633—C634 | 1.66 (18) |
N7—C5—C6—N1 | 179.21 (12) | O63—C633—C634—C635 | 179.22 (11) |
C4—C5—C6—N1 | −2.24 (17) | C632—C633—C634—C635 | −1.09 (19) |
N7—C5—C6—S6 | −2.39 (18) | C633—C634—C635—C636 | −0.5 (2) |
C4—C5—C6—S6 | 176.16 (8) | C632—C631—C636—C635 | −0.96 (18) |
C61—S6—C6—N1 | −7.88 (11) | C62—C631—C636—C635 | 179.45 (11) |
C61—S6—C6—C5 | 173.78 (9) | C634—C635—C636—C631 | 1.54 (19) |
C5—N7—C8—N9 | 0.16 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H9···N7i | 0.88 | 1.90 | 2.7715 (14) | 171 |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
S6—C6 | 1.7438 (19) | C61—C62 | 1.520 (3) |
S6—C61 | 1.8017 (18) | C62—C631 | 1.491 (3) |
C6—S6—C61 | 100.76 (9) | ||
C6—S6—C61—C62 | −178.05 (13) | S6—C61—C62—C631 | −172.56 (14) |
S6—C61—C62—O6 | 8.5 (2) |
S6—C6 | 1.741 (3) | C61—C62 | 1.510 (4) |
S6—C61 | 1.807 (3) | C62—C631 | 1.474 (3) |
C6—S6—C61 | 100.88 (12) | ||
C6—S6—C61—C62 | 170.8 (2) | S6—C61—C62—C631 | 175.8 (2) |
S6—C61—C62—O6 | −7.7 (3) |
S6—C6 | 1.7446 (18) | C61—C62 | 1.513 (2) |
S6—C61 | 1.8038 (17) | C62—C631 | 1.493 (2) |
C6—S6—C61 | 100.50 (8) | ||
C6—S6—C61—C62 | 177.77 (12) | S6—C61—C62—C631 | 177.32 (12) |
S6—C61—C62—O6 | −4.5 (2) |
S6—C6 | 1.755 (3) | C61—C62 | 1.528 (4) |
S6—C61 | 1.812 (3) | C62—C631 | 1.496 (4) |
C6—S6—C61 | 100.33 (15) | ||
C6—S6—C61—C62 | −177.8 (2) | S6—C61—C62—C631 | −178.1 (2) |
S6—C61—C62—O6 | 3.2 (4) |
S6—C6 | 1.7477 (12) | C61—C62 | 1.5162 (16) |
S6—C61 | 1.8109 (13) | C62—C631 | 1.4887 (17) |
C6—S6—C61 | 100.77 (6) | ||
C6—S6—C61—C62 | 179.54 (8) | S6—C61—C62—C631 | −175.65 (9) |
S6—C61—C62—O6 | 5.56 (14) |
θ1 is the dihedral angle between the mean planes of the purine and phenyl rings and the phenyl ring. θ2 is the dihedral angles between the mean planes of the purine ring and the plane defined by the S6/C61/C62/O6 atoms. θ3 is the dihedral angle between the mean planes of the phenyl ring and the plane defined by the S6/C61/C62/O6 atoms. |
Compound | θ1° | θ2° | θ3° |
(1) | 2.95 (7) | 8.45 (8) | 5.87 (9) |
(2) | 38.89 (9) | 17.05 (12) | 22.72 (13) |
(3) | 38.67 (6) | 14.23 (8) | 27.82 (8) |
(4) | 37.11 (10) | 13.58 (13) | 26.82 (14) |
(5) | 4.74 (5) | 5.30 (5) | 3.42 (8) |
The maximum deviations from the mean plane of the S–C–C–O bridging unit are for compounds (1)–(5) are 0.0457 (13), −0.041 (2), −0.023 (11), −0.017 (2) and 0.0302 (8) Å respectively. In all cases it is atom C42 which shows the maximum deviation. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O64i | 0.95 | 2.48 | 3.375 (3) | 157 |
C8—H8···O9ii | 0.95 | 2.37 | 3.319 (3) | 178 |
C61—H61A···O6iii | 0.99 | 2.33 | 3.269 (3) | 159 |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x−1, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O9i | 0.95 | 2.31 | 3.262 (2) | 176 |
C61—H61A···O6ii | 0.99 | 2.40 | 3.354 (2) | 162 |
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O9i | 0.95 | 2.42 | 3.367 (4) | 177 |
C61—H61B···O6ii | 0.99 | 2.45 | 3.396 (4) | 160 |
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H9···N7i | 0.88 | 1.90 | 2.7715 (14) | 171 |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
CgI(J) is plane I(J); Cg···Cg is the distance between ring centroids; α is the dihedral angle between planes I and J; CgIperp is the perpendicular distance of Cg(I) on ring J; CgJperp is the perpendicular distance of Cg(J) on ring I; Slippage is the distance between Cg(I) and the perpendicular projection of Cg(J) on ring I. Plane 1 is through the imadazole ring, plane 2 the pyrimidine ring and plane 3 the exocyclic benzene ring. |
Compound | CgI | CgJ | Cg···Cg | α | CgIperp | CgJperp | Slippage |
(1) | Cg1 | Cg3(−x, 1 − y, 1 − z) | 3.6923 (14) | 2.62 (12) | 3.4547 (9) | -3.3985 (9) | |
Cg2 | Cg3(−x, 1 − y, 1 − z) | 3.6019 (12) | 3.26 (11) | -3.3477 (9) | -3.4071 (9) | ||
(2) | Cg1 | Cg1(−x, 1 − y, −z) | 3.8561 (16) | 0.00 (15) | 3.3156 (11) | 3.3156 (11) | 1.969 |
Cg2 | Cg3(1 − x, 1/2 + y, 1/2 − z) | 3.8270 (16) | 0.80 (12) | -3.2463 (10) | -3.2391 (11) | ||
(3) | Cg1 | Cg1(−x, 1 − y, −z) | 3.7799 (11) | 0 | 3.2016 (7) | 3.2016 (7) | 2.009 |
Cg2 | Cg3(1 − x, 1/2 + y, 1/2 − z) | 4.0620 (10) | 6.70 (8) | -3.4438 (7) | -3.1708 (7) | ||
(4) | Cg1 | Cg1(1 − x, 1 − y, 1 − z) | 3.8319 (18) | 0.04 (18) | 3.1987 (13) | 3.1987 (13) | 2.110 |
Cg2 | Cg3(1 − x, 1/2 + y, 1/2 − z) | 4.1601 (18) | 6.27 (15) | -3.4328 (12) | -3.1701 (13) | ||
(5) | Cg1 | Cg3(−x, 1 − y, 1 − z) | 3.6359 (8) | 5.35 (7) | -3.4757 (5) | -3.4162 (5) | |
Cg2 | Cg3(−x, 1 − y, 1 − z) | 3.5204 (8) | 4.43 (6) | -3.3669 (5) | -3.4160 (5) |
Experimental details
(1) | (2) | (3) | |
Crystal data | |||
Chemical formula | C16H14N4O3S | C16H14N4O3S | C15H11ClN4O2S |
Mr | 342.37 | 342.37 | 346.79 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 100 | 100 | 100 |
a, b, c (Å) | 7.6343 (5), 26.2356 (18), 8.1332 (5) | 5.9920 (3), 9.9795 (5), 24.9907 (13) | 5.9900 (4), 9.9169 (7), 24.3238 (17) |
β (°) | 112.725 (2) | 95.977 (5) | 96.072 (2) |
V (Å3) | 1502.54 (17) | 1486.25 (13) | 1436.78 (17) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.24 | 0.24 | 0.43 |
Crystal size (mm) | 0.17 × 0.07 × 0.01 | 0.05 × 0.04 × 0.01 | 0.13 × 0.06 × 0.01 |
Data collection | |||
Diffractometer | Rigaku AFC12 (Right) | Rigaku AFC12 (Right) | Rigaku AFC12 (Right) |
Absorption correction | Multi-scan (CrystalClear-SM Expert; Rigaku, 20112) | Multi-scan (CrysAlis PRO; Agilent, 2014) | Multi-scan CrystalClear-SM Expert (Rigaku, 20112) |
Tmin, Tmax | 0, 1.000 | 0.439, 1.000 | 0.809, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20144, 3450, 2817 | 15437, 2619, 1852 | 18353, 3291, 2677 |
Rint | 0.089 | 0.106 | 0.050 |
(sin θ/λ)max (Å−1) | 0.649 | 0.595 | 0.651 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.148, 1.05 | 0.048, 0.116, 1.02 | 0.035, 0.092, 1.02 |
No. of reflections | 3450 | 2619 | 3291 |
No. of parameters | 219 | 219 | 209 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.81, −0.51 | 0.30, −0.36 | 0.34, −0.22 |
(4) | (5) | |
Crystal data | ||
Chemical formula | C15H11BrN4O2S | C14H12N4O2S |
Mr | 391.25 | 300.34 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 6.0705 (4), 10.0668 (7), 24.3492 (17) | 7.6683 (5), 21.8004 (15), 8.4131 (5) |
β (°) | 96.580 (2) | 107.507 (2) |
V (Å3) | 1478.19 (18) | 1341.29 (15) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.94 | 0.25 |
Crystal size (mm) | 0.15 × 0.10 × 0.02 | 0.17 × 0.12 × 0.07 |
Data collection | ||
Diffractometer | Rigaku AFC12 (Right) | Rigaku AFC12 (Right) |
Absorption correction | Multi-scan CrystalClear-SM Expert (Rigaku, 20112) | Multi-scan (CrystalClear-SM Expert; Rigaku, 2012) |
Tmin, Tmax | 0.658, 1.000 | 0.724, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18171, 3346, 2944 | 17441, 3063, 2799 |
Rint | 0.064 | 0.060 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.153, 1.06 | 0.033, 0.093, 1.03 |
No. of reflections | 3346 | 3063 |
No. of parameters | 209 | 191 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.91, −0.92 | 0.30, −0.37 |
Computer programs: CrystalClear-SM Expert (Rigaku, 2012), CrysAlis PRO (Agilent, 2014), OSCAIL (McArdle et al., 2004) and SHELXT (Sheldrick, 2015a), OSCAIL (McArdle et al., 2004), ShelXle (Hübschle et al., 2011) and SHELXL2014 (Sheldrick, 2015b), Mercury (Macrae et al., 2006), SHELXL2014 (Sheldrick, 2015b) 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) for financial support. FC (grant SFRH/BPD/74491/2010) is supported by FCT, POPH and QREN.
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