research communications
Crystal structures of four chiral imine-substituted thiophene derivatives
aLaboratorio de Síntesis de Complejos, Facultad de Ciencias Químicas, Universidad Autónoma de Puebla, A.P. 1067, 72001 Puebla, Pue., Mexico, bInstituto de Física, Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico, and cCentro de Química, Instituto de Ciencias, Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com
A series of thiophenes substituted in positions 2 and 5 by imine groups have been synthesized using a solvent-free approach, and their crystal structures determined. The substituents are chiral groups, and the expected S)-(+)-(1,2,3,4-tetrahydronaphthalen-1-yl)imino]thiophene, C26H26N2S, (I), 2,5-bis{[(R)-(−)-1-(4-methoxyphenyl)ethyl]iminomethyl}thiophene, C24H26N2O2S, (II), 2,5-bis{[(R)-(−)-1-(4-fluorophenyl)ethyl]iminomethyl}thiophene, C22H20F2N2S, (III), and 2,5-bis{[(S)-(+)-1-(4-chlorophenyl)ethyl]iminomethyl}thiophene, C22H20Cl2N2S, (IV). A common feature of all four molecules is the presence of twofold symmetry. For (I), which crystallizes in the triclinic P1, this symmetry is non-crystallographic, but for (II) in C2 and the (III) and (IV) that crystallize in P21212, the twofold symmetry is crystallographically imposed with one half of each molecule in the The comparable molecular symmetry in the four structures is also reflected in similar packing, with molecules aggregated to form chains through weak C—H⋯S interactions.
for each molecule was confirmed by of the The compounds are 2,5-bis[(Keywords: crystal structure; Schiff base; bis-imine; thiophene.
1. Chemical context
Thiophenedicarbaldehydes have a variety of applications (Dean, 1982a,b), for instance in the synthesis of annulenones and polyenyl-substituted thiophenes (Sargent & Cresp, 1975), in the preparation of macrocyclic ligands for bimetallic complexes that are able to mimic enzymes (Nelson et al., 1983), in crown ether chemistry (Cram & Trueblood, 1981) and, more recently, in the preparation of for photovoltaic applications (Bolduc et al., 2013a,b; Petrus et al., 2014). In regard to this latter application, most of the conjugated materials used in organic electronics are synthesized using time-consuming Suzuki-, Wittig-, or Heck-type coupling reactions that require expensive catalysts, stringent reaction conditions, and tedious purification processes. In order to afford a more economic route towards organic photovoltaic materials, derived from 2,5-thiophenedicarbaldehyde as the conjugated linker unit have recently been used. The azomethine bond, which is isoelectronic with the vinyl bond and possesses similar optoelectronic and thermal properties, is easily accessible through the Schiff condensation under near ambient reaction conditions (Morgan et al., 1987; Pérez Guarìn et al., 2007; Sicard et al., 2013).
We report here the synthesis and X-ray characterization of such thiophene derivatives, as a continuation of a partially published record (Bernès et al., 2013; Mendoza et al., 2014). We are improving a general solvent-free approach for these syntheses, recognising that ecological aspects in organic chemistry have become a priority, in order to minimize the quantity of toxic waste and by-products, and to decrease the amount of solvent in the reaction media or during work-up (Tanaka & Toda, 2000; Noyori, 2005).
In the synthesis of the thiophenes reported here, the Schiff condensation generates a single by-product, water, and a one-step recrystallization affords the pure substituted thiophene in nearly quantitative yields. Our protocol may be readily extended to any low molecular weight 2,5-susbtituted thiophene, providing that a liquid amine is used for the condensation. In the present work, the starting material is 2,5-thiophenedicarbaldehyde, a low melting-point compound (m.p. = 388–390 K), and four chiral
were used. We took advantage of the of the sulfur sites to confirm that the configuration of the chiral amine is retained during the condensation.2. Structural commentary
The first compound was synthesized using (S)-(+)-1-aminotetraline. The Schiff base (I), C26H26N2S, crystallizes in the P1, with the expected (Fig. 1). The general shape of the molecule displays a pseudo-twofold axis, passing through the S atom and the midpoint of the thiophene C—C σ-bond. As a consequence, the independent benzene rings are placed above and below the thiophene ring, and are inclined to one another at a dihedral angle of 73.76 (15)°. The central core containing the thiophene ring and the imine bonds is virtually planar, and the imine bonds are substituted by the tetralin ring systems, which present the same conformation. The aliphatic rings C9–C13/C18 and C19–C23/C28 each have a half-chair conformation.
Compound (II), C24H26N2O2S, was obtained using (R)-(+)-(4-methoxy)phenylethylamine as the chiral component in the Schiff condensation. The twofold molecular axis, which was a latent symmetry in the case of (I), is a true in (II), and this compound crystallizes in the C2 (Fig. 2). The thus contains half a molecule, and the molecular conformation for the complete molecule is similar to that of (I). The benzene rings have a free relative orientation, since these rings are not fused in a bicyclic system, as in (I); the dihedral angle between symmetry-related rings is 61.30 (7)°.
Compounds (III) and (IV), synthesized with enantiomerically pure (4-halogen)phenylethylamines (halogen = F, Cl) are isomorphous and crystallize with orthorhombic unit cells. The latent twofold symmetry of (I) is again observed, since both molecules lie on the crystallographic twofold axes of the P21212 (Fig. 3). The dihedral angle between the benzene rings is close to that observed for (II): 64.18 (8)° for (III) and 62.03 (9)° for (IV). The same Schiff base but with Br as the halogen substituent has been published previously (Mendoza et al., 2014), but is not isomorphous with (III) and (IV). Instead, this molecule was found to crystallize in the C2, with unit-cell parameters and a very similar to those of (II). A systematic trend is thus emerging for these 2,5-substituted thiophenes, related to the potential twofold molecular symmetry: they have a strong tendency to crystallize in space groups that include at least one C2 axis, such as C2 and P21212 for the chiral crystals. This trend extends to achiral molecules, which also have twofold in the C2/c (Kudyakova et al., 2011; Suganya et al., 2014; Boyle et al., 2015; Moussallem et al., 2015). The features shared by these related compounds could also be a signature of a propensity towards between monoclinic and orthorhombic systems.
The difference between and exact C2 molecular symmetry in (II)–(IV) is also reflected in the degree of conjugation between thiophene rings and imine bonds. For (I), dihedral angles between the thiophene and C=N—C* mean planes (C* is the chiral C atom bonded to the imine functionality) are 6.9 (7) and 1.9 (6)°. Other crystals have a symmetry restriction, inducing a small deconjugation of the imine bonds. The corresponding dihedral angles with the thiophene rings are 8.5 (4), 10.1 (3), and 9.8 (3)°, for (II), (III) and (IV), respectively.
in (I)3. Supramolecular features
Although all compounds have benzene rings, neither π–π nor C—H⋯π contacts stabilize the crystal structures. However, these compounds share a common supramolecular feature. Lone pairs of S atoms interact with thiophenic CH groups of a neighboring molecule in the crystal, forming chains along the short cell axes: [100] for (I), [010] for (II) and [001] for (III) and (IV). An example is presented in Fig. 4, for compound (II). These bifurcated S⋯C—H contacts have a significant strength for (I), perhaps as a consequence of the relaxed molecular symmetry in P1. The contacts are weaker for (II), (III) and (IV), which have a geometry restrained by the (Table 1).
4. Database survey
Many thiophenes substituted in the 2 and 5 positions by imine groups have been characterized; however, almost all were achiral compounds. X-ray structures have been reported mostly in C2/c (Suganya et al., 2014; Kudyakova et al., 2011, 2012; Bolduc et al., 2013b). Other represented space groups for achiral molecules are P21 (Skene & Dufresne, 2006) and P21/c (Wiedermann et al., 2005). Finally, a single case of a molecule presenting mirror symmetry has been described (Fridman & Kaftory, 2007), in Pnma.
The group of chiral molecules belonging to this family is much less populated, with two examples reported by our group in this journal. Both are molecules with the C2 and crystallize in space groups C2 (Mendoza et al., 2014) and P22121 (Bernès et al., 2013).
5. Synthesis and crystallization
Synthesis. The chiral used for the Schiff condensation were obtained directly from suppliers: (S)-(+)-1,2,3,4-tetrahydro-1-naphthylamine for (I), (R)-(+)-1-(4-methoxyphenyl)ethylamine for (II), (R)-(+)-1-(4-fluorophenyl)ethylamine for (III) and (S)-(−)-1-(4-chlorophenyl)ethylamine for (IV). 2,5-Thiophenedicarbaldehyde (100 mg, 0.71 mmol) and the chiral amine (1.4 mmol) in a 1:2 molar ratio were mixed at room temperature under solvent-free conditions, giving light-yellow (II and IV), colorless (III) or light-brown (IV) solids, in 95-97% yields. The crude solids were recrystallized from CH2Cl2, affording colorless crystals of (I)–(IV).
Spectroscopy. (I): m.p. 437–438 K. [α]20D = +655.4 (c = 1, CHCl3). FTIR: 1616 cm−1 (C=N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.76–1.86 (m, 2H; H-al), 1.96–2.06 (m, 6H; H-al), 2.74–2.90 (m, 4H; H-al), 4.51 (t, 2H; H-al), 6.98–7.02 (m, 2H; H-ar), 7.09–7.15 (m, 6H; H-ar), 7.28 (s, 2H; H-ar), 8.36 (s, 2H; HC=N). 13C NMR: δ = 19.7, 29.3, 31.1, 67.7 (C-al), 125.7, 126.9, 128.7, 129.1, 129.6, 136.8, 137.1, 145.1 (C-ar), 153.1 (HC=N). MS–EI: m/z = 398 (M+).
(II): m.p. 405–406 K. [α]20D = −626.8 (c = 1, CHCl3). FTIR: 1631 cm−1 (C=N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.53 (d, 6H; CHCH3), 3.78 (s, 6H; OCH3), 4.47 (q, 2H; CHCH3), 6.85–6.88 (m, 4H; H-ar), 7.19 (s, 2H; H-ar), 7.29–7.32 (m, 4H; H-ar), 8.33 (s, 2H; HC=N). 13C NMR: δ = 24.8 (CHCH3), 55.2 (OCH3), 68.1 (CHCH3), 113.7, 127.6, 129.6, 137.1, 145.2, 152.1 (C-ar), 158.5 (HC=N). MS–EI: m/z = 406 (M+).
(III): m.p. 420–421 K. [α]20D = −542.5 (c = 1, CHCl3). FTIR: 1621 cm−1 (C=N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.53 (d, 6H; CHCH3), 4.49 (q, 2H; CHCH3), 7.00–7.38 (m, 10H; H-ar), 8.37 (s, 2H; HC=N). 13C NMR: δ = 25.2 (CHCH3), 68.7 (CHCH3), 115.2 (d, JF-C = 21.2 Hz; C-ar), 128.1 (d, JF-C = 8.7 Hz; C-ar), 130.1 (C-ar), 140.7 (d, JF-C = 2.5 Hz; C-ar), 145.1 (C-ar), 161.1 (d, JF-C = 242.5 Hz; C-ar), 152.5 (HC=N). MS–EI: m/z = 382 (M+).
(IV): m.p. 434–435 K. [α]20D = +726.5 (c = 1, CHCl3). FTIR: 1623 cm−1 (C=N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.53 (d, 6H; CHCH3), 4.48 (q, 2H; CHCH3), 7.23–7.35 (m, 10H; H-ar), 8.37 (s, 2H; HC=N). 13C NMR: δ = 25.2 (CHCH3), 68.7 (CHCH3), 128.0, 128.6, 130.2, 132.5, 143.5, 145.1 (C-ar), 152.7 (HC=N).
6. Refinement
Crystal data, data collection and structure . No unusual issues appeared, and refinements were carried out on non-restricted models. All H atoms were placed in calculated positions, and refined as riding on their carrier C atoms, with C—H bond lengths fixed to 0.93 (aromatic CH), 0.96 (methyl CH3), 0.97 (methylene CH2), or 0.98 Å (methine CH). Isotropic displacement parameters were calculated as Uiso(H) = 1.5Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(C) for other H atoms. For all compounds, the was based on the of the (Parsons et al., 2013), confirming that the configuration of the chiral amine used as the starting material was retained during the Schiff condensation.
details are summarized in Table 2
|
Supporting information
10.1107/S2056989016002516/sj5495sup1.cif
contains datablocks I, II, III, IV, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016002516/sj5495Isup2.hkl
Structure factors: contains datablock II. DOI: 10.1107/S2056989016002516/sj5495IIsup3.hkl
Structure factors: contains datablock III. DOI: 10.1107/S2056989016002516/sj5495IIIsup4.hkl
Structure factors: contains datablock IV. DOI: 10.1107/S2056989016002516/sj5495IVsup5.hkl
Supporting information file. DOI: 10.1107/S2056989016002516/sj5495Isup6.cml
Supporting information file. DOI: 10.1107/S2056989016002516/sj5495IIsup7.cml
Supporting information file. DOI: 10.1107/S2056989016002516/sj5495IIIsup8.cml
Supporting information file. DOI: 10.1107/S2056989016002516/sj5495IVsup9.cml
Thiophenedicarbaldehydes have a variety of applications (Dean, 1982a,b), for instance in the synthesis of annulenones and polyenyl-substituted thiophenes (Sargent & Cresp, 1975), in the preparation of macrocyclic ligands for bimetallic complexes that are able to mimic enzymes (Nelson et al., 1983), in crown ether chemistry (Cram & Trueblood, 1981) and, more recently, in the preparation of
for photovoltaic applications (Bolduc et al., 2013a,b; Petrus et al., 2014). In regard to this latter application, most of the conjugated materials used in organic electronics are synthesized using time-consuming Suzuki-, Wittig-, or Heck-type coupling reactions that require expensive catalysts, stringent reaction conditions, and tedious purification processes. In order to afford a more economic route towards organic photovoltaic materials, derived from 2,5-thiophenedicarbaldehyde as the conjugated linker unit have recently been used. The azomethine bond, which is isoelectronic with the vinyl bond and possesses similar optoelectronic and thermal properties, is easily accessible through the Schiff condensation under near ambient reaction conditions (Morgan et al., 1987; Pérez Guarìn et al., 2007; Sicard et al., 2013).We report here the synthesis and X-ray characterization of such thiophene derivatives, as a continuation of a partially published record (Bernès et al., 2013; Mendoza et al., 2014). We are improving a general solvent-free approach for these syntheses, recognizing that ecological aspects in organic chemistry have become a priority, in order to minimize the quantity of toxic waste and by-products, and to decrease the amount of solvent in the reaction media or during work-up (Tanaka & Toda, 2000; Noyori, 2005).
In the synthesis of the thiophenes reported here, the Schiff condensation generates a single by-product, water, and a one-step recrystallization affords the pure substituted thiophene in nearly quantitative yields. Our protocol may be readily extended to any low molecular weight 2,5-susbtituted thiophene, providing that a liquid amine is used for the condensation. In the present work, the starting material is 2,5-thiophenedicarbaldehyde, a low melting-point compound (m.p. = 388–390 K), and four chiral
were used. We took advantage of the of the sulfur sites to confirm that the configuration of the chiral amine is retained during the condensation.The first compound was synthesized using (S)-(+)-1-aminotetraline. The Schiff base (I), C26H26N2S, crystallizes in the σ-bond. As a consequence, the independent benzene rings are placed above and below the thiophene ring, and are inclined to one another at a dihedral angle of 73.76 (15)°. The central core containing the thiophene ring and the imine bonds is virtually planar, and the imine bonds are substituted by the tetralin ring systems, which present the same conformation. The aliphatic rings C9–C13/C18 and C19–C23/C28 each have a half-chair conformation.
P1, with the expected (Fig. 1). The general shape of the molecule displays a pseudo-twofold axis, passing through the S atom and the midpoint of the thiophene C—CCompound (II), C24H26N2O2S, was obtained using (R)-(+)-(4-methoxy)phenylethylamine as the chiral component in the Schiff condensation. The twofold molecular axis, which was a latent symmetry in the case of (I), is a true
in (II), and this compound crystallizes in the C2 (Fig. 2). The thus contains half a molecule, and the for the complete molecule is similar to that of (I). The benzene rings have a free relative orientation, since these rings are not fused in a bicyclic system, as in (I); the dihedral angle between symmetry-related rings is 61.30 (7)°.Compounds (III) and (IV), synthesized with enantiomerically pure (4-halogen)phenylethylamines (halogen = F, Cl) are isomorphous and crystallize with orthorhombic unit cells. The latent twofold symmetry of (I) is again observed, since both molecules lie on the crystallographic twofold axes of the
P21212 (Fig. 3). The dihedral angle between the benzene rings is close to that observed for (II): 64.18 (8)° for (III) and 62.03 (9)° for (IV). The same Schiff base but with Br as the halogen substituent has been published previously (Mendoza et al., 2014), but is not isomorphous with (III) and (IV). Instead, this molecule was found to crystallize in the C2, with unit-cell parameters and a very similar to those of (II). A systematic trend is thus emerging for these 2,5-substituted thiophenes, related to the potential twofold molecular symmetry: they have a strong tendency to crystallize in space groups that include at least one C2 axis, such as C2 and P21212 for the chiral crystals. This trend extends to achiral molecules, which also have twofold in the C2/c (Kudyakova et al., 2011; Suganya et al., 2014; Boyle et al., 2015; Moussallem et al., 2015). The features shared by these related compounds could also be a signature of a propensity towards between monoclinic and orthorhombic systems.The difference between ═N—C* mean planes (C* is the chiral C atom bonded to the imine functionality) are 6.9 (7) and 1.9 (6)°. Other crystals have a symmetry restriction, inducing a small deconjugation of the imine bonds. The corresponding dihedral angles with the thiophene rings are 8.5 (4), 10.1 (3), and 9.8 (3)°, for (II), (III) and (IV), respectively.
in (I) and exact C2 molecular symmetry in (II)–(IV) is also reflected in the degree of conjugation between thiophene rings and imine bonds. For (I), dihedral angles between the thiophene and CAlthough all compounds have benzene rings, neither π–π nor C—H···π contacts stabilize the crystal structures. However, these compounds share a common supramolecular feature. Lone pairs of S atoms interact with thiophenic CH groups of a neighboring molecule in the crystal, forming chains along the short cell axes: [100] for (I), [010] for (II) and [001] for (III) and (IV). An example is presented in Fig. 4, for compound (II). These bifurcated S···C—H contacts have a significant strength for (I), perhaps as a consequence of the relaxed molecular symmetry in P1. The contacts are weaker for (II), (III) and (IV), which have a geometry restrained by the (Table 1).
Many thiophenes substituted in the 2 and 5 positions by imine groups have been characterized; however, almost all were achiral compounds. X-ray structures have been reported mostly in
C2/c (Suganya et al., 2014; Kudyakova et al., 2011, 2012; Bolduc et al., 2013b). Other represented space groups for achiral molecules are P21 (Skene & Dufresne, 2006) and P21/c (Wiedermann et al., 2005). Finally, a single case of a molecule presenting mirror symmetry has been described (Fridman & Kaftory, 2007), in Pnma.The group of chiral molecules belonging to this family is much less populated, with two examples reported by our group in this journal. Both are molecules with the C2
and crystallize in space groups C2 (Mendoza et al., 2014) and P22121 (Bernès et al., 2013).Synthesis. The chiral
used for the Schiff condensation were obtained directly from suppliers: (S)-(+)-1,2,3,4-tetrahydro-1-naphthylamine for (I), (R)-(+)-1-(4-methoxyphenyl)ethylamine for (II), (R)-(+)-1-(4-fluorophenyl)ethylamine for (III) and (S)-(-)-1-(4-chlorophenyl)ethylamine for (IV). 2,5-Thiophenedicarbaldehyde (100 mg, 0.71 mmol) and the chiral amine (1.4 mmol) in a 1:2 molar ratio were mixed at room temperature under solvent-free conditions, giving light yellow (II and IV), colorless (III) or light brown (IV) solids, in 95–97% yields. The crude solids were recrystallized from CH2Cl2, affording colorless crystals of (I)–(IV).Spectroscopy. (I): m.p. 1437–438 K. [α]20D = +655.4 (c =1, CHCl3). FTIR: 1616 cm−1 (C═N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.76–1.86 (m, 2H; H-al), 1.96–2.06 (m, 6H; H-al), 2.74–2.90 (m, 4H; H-al), 4.51 (t, 2H; H-al), 6.98–7.02 (m, 2H; H-ar), 7.09–7.15 (m, 6H; H-ar), 7.28 (s, 2H; H-ar), 8.36 (s, 2H; HC═N). 13C-NMR: δ = 19.7, 29.3, 31.1, 67.7 (C-al), 125.7, 126.9, 128.7, 129.1, 129.6, 136.8, 137.1, 145.1 (C-ar), 153.1 (HC═N). MS–EI: m/z = 398 (M+).
(II): m.p. 405–406 K. [α]20D = −626.8 (c =1, CHCl3). FTIR: 1631 cm−1 (C═N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.53 (d, 6H; CHCH3), 3.78 (s, 6H; OCH3), 4.47 (q, 2H; CHCH3), 6.85–6.88 (m, 4H; H-ar), 7.19 (s, 2H; H-ar), 7.29–7.32 (m, 4H; H-ar), 8.33 (s, 2H; HC═N). 13C-NMR: δ = 24.8 (CHCH3), 55.2 (OCH3), 68.1 (CHCH3), 113.7, 127.6, 129.6, 137.1, 145.2, 152.1 (C-ar), 158.5 (HC═N). MS–EI: m/z = 406 (M+).
(III): m.p. 420–421 K. [α]20D = −542.5 (c =1, CHCl3). FTIR: 1621 cm−1 (C═N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.53 (d, 6H; CHCH3), 4.49 (q, 2H; CHCH3), 7.00–7.38 (m, 10H; H-ar), 8.37 (s, 2H; HC═N). 13C-NMR: δ = 25.2 (CHCH3), 68.7 (CHCH3), 115.2 (d, JF—C = 21.2 Hz; C-ar), 128.1 (d, JF—C = 8.7 Hz; C-ar), 130.1 (C-ar), 140.7 (d, JF—C = 2.5 Hz; C-ar), 145.1 (C-ar), 161.1 (d, JF—C = 242.5 Hz; C-ar), 152.5 (HC═N). MS–EI: m/z = 382 (M+).
(IV): m.p. 434–435 K. [α]20D = +726.5 (c =1, CHCl3). FTIR: 1623 cm−1 (C═N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.53 (d, 6H; CHCH3), 4.48 (q, 2H; CHCH3), 7.23–7.35 (m, 10H; H-ar), 8.37 (s, 2H; HC═N). 13C-NMR: δ = 25.2 (CHCH3), 68.7 (CHCH3), 128.0, 128.6, 130.2, 132.5, 143.5, 145.1 (C-ar), 152.7 (HC═N).
Crystal data, data collection and structure
details are summarized in Table 2. No unusual issues appeared, and refinements were carried out on non-restricted models. All H atoms were placed in calculated positions, and refined as riding on their carrier C atoms, with C—H bond lengths fixed to 0.93 (aromatic CH), 0.96 (methyl CH3), 0.97 (methylene CH2), or 0.98 Å (methine CH). Isotropic displacement parameters were calculated as Uiso(H) = 1.5×Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(C) for other H atoms. For all compounds, the was based on the of the (Parsons et al., 2013), confirming that the configuration of the chiral amine used as the starting material was retained during the Schiff condensation.Thiophenedicarbaldehydes have a variety of applications (Dean, 1982a,b), for instance in the synthesis of annulenones and polyenyl-substituted thiophenes (Sargent & Cresp, 1975), in the preparation of macrocyclic ligands for bimetallic complexes that are able to mimic enzymes (Nelson et al., 1983), in crown ether chemistry (Cram & Trueblood, 1981) and, more recently, in the preparation of
for photovoltaic applications (Bolduc et al., 2013a,b; Petrus et al., 2014). In regard to this latter application, most of the conjugated materials used in organic electronics are synthesized using time-consuming Suzuki-, Wittig-, or Heck-type coupling reactions that require expensive catalysts, stringent reaction conditions, and tedious purification processes. In order to afford a more economic route towards organic photovoltaic materials, derived from 2,5-thiophenedicarbaldehyde as the conjugated linker unit have recently been used. The azomethine bond, which is isoelectronic with the vinyl bond and possesses similar optoelectronic and thermal properties, is easily accessible through the Schiff condensation under near ambient reaction conditions (Morgan et al., 1987; Pérez Guarìn et al., 2007; Sicard et al., 2013).We report here the synthesis and X-ray characterization of such thiophene derivatives, as a continuation of a partially published record (Bernès et al., 2013; Mendoza et al., 2014). We are improving a general solvent-free approach for these syntheses, recognizing that ecological aspects in organic chemistry have become a priority, in order to minimize the quantity of toxic waste and by-products, and to decrease the amount of solvent in the reaction media or during work-up (Tanaka & Toda, 2000; Noyori, 2005).
In the synthesis of the thiophenes reported here, the Schiff condensation generates a single by-product, water, and a one-step recrystallization affords the pure substituted thiophene in nearly quantitative yields. Our protocol may be readily extended to any low molecular weight 2,5-susbtituted thiophene, providing that a liquid amine is used for the condensation. In the present work, the starting material is 2,5-thiophenedicarbaldehyde, a low melting-point compound (m.p. = 388–390 K), and four chiral
were used. We took advantage of the of the sulfur sites to confirm that the configuration of the chiral amine is retained during the condensation.The first compound was synthesized using (S)-(+)-1-aminotetraline. The Schiff base (I), C26H26N2S, crystallizes in the σ-bond. As a consequence, the independent benzene rings are placed above and below the thiophene ring, and are inclined to one another at a dihedral angle of 73.76 (15)°. The central core containing the thiophene ring and the imine bonds is virtually planar, and the imine bonds are substituted by the tetralin ring systems, which present the same conformation. The aliphatic rings C9–C13/C18 and C19–C23/C28 each have a half-chair conformation.
P1, with the expected (Fig. 1). The general shape of the molecule displays a pseudo-twofold axis, passing through the S atom and the midpoint of the thiophene C—CCompound (II), C24H26N2O2S, was obtained using (R)-(+)-(4-methoxy)phenylethylamine as the chiral component in the Schiff condensation. The twofold molecular axis, which was a latent symmetry in the case of (I), is a true
in (II), and this compound crystallizes in the C2 (Fig. 2). The thus contains half a molecule, and the for the complete molecule is similar to that of (I). The benzene rings have a free relative orientation, since these rings are not fused in a bicyclic system, as in (I); the dihedral angle between symmetry-related rings is 61.30 (7)°.Compounds (III) and (IV), synthesized with enantiomerically pure (4-halogen)phenylethylamines (halogen = F, Cl) are isomorphous and crystallize with orthorhombic unit cells. The latent twofold symmetry of (I) is again observed, since both molecules lie on the crystallographic twofold axes of the
P21212 (Fig. 3). The dihedral angle between the benzene rings is close to that observed for (II): 64.18 (8)° for (III) and 62.03 (9)° for (IV). The same Schiff base but with Br as the halogen substituent has been published previously (Mendoza et al., 2014), but is not isomorphous with (III) and (IV). Instead, this molecule was found to crystallize in the C2, with unit-cell parameters and a very similar to those of (II). A systematic trend is thus emerging for these 2,5-substituted thiophenes, related to the potential twofold molecular symmetry: they have a strong tendency to crystallize in space groups that include at least one C2 axis, such as C2 and P21212 for the chiral crystals. This trend extends to achiral molecules, which also have twofold in the C2/c (Kudyakova et al., 2011; Suganya et al., 2014; Boyle et al., 2015; Moussallem et al., 2015). The features shared by these related compounds could also be a signature of a propensity towards between monoclinic and orthorhombic systems.The difference between ═N—C* mean planes (C* is the chiral C atom bonded to the imine functionality) are 6.9 (7) and 1.9 (6)°. Other crystals have a symmetry restriction, inducing a small deconjugation of the imine bonds. The corresponding dihedral angles with the thiophene rings are 8.5 (4), 10.1 (3), and 9.8 (3)°, for (II), (III) and (IV), respectively.
in (I) and exact C2 molecular symmetry in (II)–(IV) is also reflected in the degree of conjugation between thiophene rings and imine bonds. For (I), dihedral angles between the thiophene and CAlthough all compounds have benzene rings, neither π–π nor C—H···π contacts stabilize the crystal structures. However, these compounds share a common supramolecular feature. Lone pairs of S atoms interact with thiophenic CH groups of a neighboring molecule in the crystal, forming chains along the short cell axes: [100] for (I), [010] for (II) and [001] for (III) and (IV). An example is presented in Fig. 4, for compound (II). These bifurcated S···C—H contacts have a significant strength for (I), perhaps as a consequence of the relaxed molecular symmetry in P1. The contacts are weaker for (II), (III) and (IV), which have a geometry restrained by the (Table 1).
Many thiophenes substituted in the 2 and 5 positions by imine groups have been characterized; however, almost all were achiral compounds. X-ray structures have been reported mostly in
C2/c (Suganya et al., 2014; Kudyakova et al., 2011, 2012; Bolduc et al., 2013b). Other represented space groups for achiral molecules are P21 (Skene & Dufresne, 2006) and P21/c (Wiedermann et al., 2005). Finally, a single case of a molecule presenting mirror symmetry has been described (Fridman & Kaftory, 2007), in Pnma.The group of chiral molecules belonging to this family is much less populated, with two examples reported by our group in this journal. Both are molecules with the C2
and crystallize in space groups C2 (Mendoza et al., 2014) and P22121 (Bernès et al., 2013).Synthesis. The chiral
used for the Schiff condensation were obtained directly from suppliers: (S)-(+)-1,2,3,4-tetrahydro-1-naphthylamine for (I), (R)-(+)-1-(4-methoxyphenyl)ethylamine for (II), (R)-(+)-1-(4-fluorophenyl)ethylamine for (III) and (S)-(-)-1-(4-chlorophenyl)ethylamine for (IV). 2,5-Thiophenedicarbaldehyde (100 mg, 0.71 mmol) and the chiral amine (1.4 mmol) in a 1:2 molar ratio were mixed at room temperature under solvent-free conditions, giving light yellow (II and IV), colorless (III) or light brown (IV) solids, in 95–97% yields. The crude solids were recrystallized from CH2Cl2, affording colorless crystals of (I)–(IV).Spectroscopy. (I): m.p. 1437–438 K. [α]20D = +655.4 (c =1, CHCl3). FTIR: 1616 cm−1 (C═N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.76–1.86 (m, 2H; H-al), 1.96–2.06 (m, 6H; H-al), 2.74–2.90 (m, 4H; H-al), 4.51 (t, 2H; H-al), 6.98–7.02 (m, 2H; H-ar), 7.09–7.15 (m, 6H; H-ar), 7.28 (s, 2H; H-ar), 8.36 (s, 2H; HC═N). 13C-NMR: δ = 19.7, 29.3, 31.1, 67.7 (C-al), 125.7, 126.9, 128.7, 129.1, 129.6, 136.8, 137.1, 145.1 (C-ar), 153.1 (HC═N). MS–EI: m/z = 398 (M+).
(II): m.p. 405–406 K. [α]20D = −626.8 (c =1, CHCl3). FTIR: 1631 cm−1 (C═N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.53 (d, 6H; CHCH3), 3.78 (s, 6H; OCH3), 4.47 (q, 2H; CHCH3), 6.85–6.88 (m, 4H; H-ar), 7.19 (s, 2H; H-ar), 7.29–7.32 (m, 4H; H-ar), 8.33 (s, 2H; HC═N). 13C-NMR: δ = 24.8 (CHCH3), 55.2 (OCH3), 68.1 (CHCH3), 113.7, 127.6, 129.6, 137.1, 145.2, 152.1 (C-ar), 158.5 (HC═N). MS–EI: m/z = 406 (M+).
(III): m.p. 420–421 K. [α]20D = −542.5 (c =1, CHCl3). FTIR: 1621 cm−1 (C═N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.53 (d, 6H; CHCH3), 4.49 (q, 2H; CHCH3), 7.00–7.38 (m, 10H; H-ar), 8.37 (s, 2H; HC═N). 13C-NMR: δ = 25.2 (CHCH3), 68.7 (CHCH3), 115.2 (d, JF—C = 21.2 Hz; C-ar), 128.1 (d, JF—C = 8.7 Hz; C-ar), 130.1 (C-ar), 140.7 (d, JF—C = 2.5 Hz; C-ar), 145.1 (C-ar), 161.1 (d, JF—C = 242.5 Hz; C-ar), 152.5 (HC═N). MS–EI: m/z = 382 (M+).
(IV): m.p. 434–435 K. [α]20D = +726.5 (c =1, CHCl3). FTIR: 1623 cm−1 (C═N). 1H NMR (500 MHz, CHCl3/TMS): δ = 1.53 (d, 6H; CHCH3), 4.48 (q, 2H; CHCH3), 7.23–7.35 (m, 10H; H-ar), 8.37 (s, 2H; HC═N). 13C-NMR: δ = 25.2 (CHCH3), 68.7 (CHCH3), 128.0, 128.6, 130.2, 132.5, 143.5, 145.1 (C-ar), 152.7 (HC═N).
detailsCrystal data, data collection and structure
details are summarized in Table 2. No unusual issues appeared, and refinements were carried out on non-restricted models. All H atoms were placed in calculated positions, and refined as riding on their carrier C atoms, with C—H bond lengths fixed to 0.93 (aromatic CH), 0.96 (methyl CH3), 0.97 (methylene CH2), or 0.98 Å (methine CH). Isotropic displacement parameters were calculated as Uiso(H) = 1.5×Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(C) for other H atoms. For all compounds, the was based on the of the (Parsons et al., 2013), confirming that the configuration of the chiral amine used as the starting material was retained during the Schiff condensation.For all compounds, data collection: CrysAlis PRO (Agilent, 2013); cell
CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SHELXT (Sheldrick, 2015a) for (II), (III), (IV). For all compounds, program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).Fig. 1. The molecular structure of (I), with displacement ellipsoids for non-H atoms at the 30% probability level. | |
Fig. 2. The molecular structure of (II), with displacement ellipsoids for non-H atoms at the 30% probability level. Non-labeled atoms are generated by symmetry code (1 − x, y, 1 − z). | |
Fig. 3. The molecular structures of isomorphous compounds (III) and (IV), with displacement ellipsoids for non-H atoms at the 30% probability level. Notice the different configuration for chiral center C5 in (III) and (IV). Non-labeled atoms are generated by symmetry codes (1 − x, −y, z) and (1 − x, 2 − y, z) for (III) and (IV), respectively. | |
Fig. 4. Part of the crystal structure of (II), showing C—H···S hydrogen bonds (dashed lines) linking molecules along [010]. [Symmetry codes: (i) 1 − x, y, 1 − z; (ii) x, 1 + y, z.] |
C26H26N2S | F(000) = 212 |
Mr = 398.55 | Dx = 1.187 Mg m−3 |
Triclinic, P1 | Melting point: 437 K |
a = 5.9093 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.6258 (5) Å | Cell parameters from 2148 reflections |
c = 12.6570 (8) Å | θ = 3.3–22.6° |
α = 87.802 (5)° | µ = 0.16 mm−1 |
β = 78.329 (5)° | T = 298 K |
γ = 87.427 (5)° | Plate, colorless |
V = 557.76 (6) Å3 | 0.34 × 0.12 × 0.06 mm |
Z = 1 |
Agilent Xcalibur (Atlas, Gemini) diffractometer | 4036 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2958 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 10.5564 pixels mm-1 | θmax = 26.1°, θmin = 3.1° |
ω scans | h = −7→7 |
Absorption correction: analytical CrysAlis PRO, (Agilent, 2013) | k = −9→9 |
Tmin = 0.969, Tmax = 0.992 | l = −15→15 |
6689 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.058 | H-atom parameters constrained |
wR(F2) = 0.127 | w = 1/[σ2(Fo2) + (0.0525P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
4036 reflections | Δρmax = 0.31 e Å−3 |
262 parameters | Δρmin = −0.19 e Å−3 |
3 restraints | Absolute structure: Flack x determined using 962 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
0 constraints | Absolute structure parameter: −0.12 (7) |
Primary atom site location: structure-invariant direct methods |
C26H26N2S | γ = 87.427 (5)° |
Mr = 398.55 | V = 557.76 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.9093 (4) Å | Mo Kα radiation |
b = 7.6258 (5) Å | µ = 0.16 mm−1 |
c = 12.6570 (8) Å | T = 298 K |
α = 87.802 (5)° | 0.34 × 0.12 × 0.06 mm |
β = 78.329 (5)° |
Agilent Xcalibur (Atlas, Gemini) diffractometer | 4036 independent reflections |
Absorption correction: analytical CrysAlis PRO, (Agilent, 2013) | 2958 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.992 | Rint = 0.040 |
6689 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | H-atom parameters constrained |
wR(F2) = 0.127 | Δρmax = 0.31 e Å−3 |
S = 1.02 | Δρmin = −0.19 e Å−3 |
4036 reflections | Absolute structure: Flack x determined using 962 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
262 parameters | Absolute structure parameter: −0.12 (7) |
3 restraints |
x | y | z | Uiso*/Ueq | ||
S1 | 0.66581 (19) | 0.49640 (17) | 0.11819 (12) | 0.0488 (4) | |
N1 | 0.5097 (7) | 0.7980 (6) | 0.2625 (3) | 0.0507 (12) | |
C2 | 0.7239 (10) | 0.7657 (7) | 0.2474 (4) | 0.0490 (13) | |
H2A | 0.8132 | 0.8300 | 0.2834 | 0.059* | |
C3 | 0.8355 (8) | 0.6297 (7) | 0.1747 (4) | 0.0469 (13) | |
C4 | 1.0622 (9) | 0.5892 (7) | 0.1402 (5) | 0.0575 (15) | |
H4A | 1.1792 | 0.6461 | 0.1628 | 0.069* | |
C5 | 1.1042 (8) | 0.4510 (7) | 0.0658 (5) | 0.0595 (15) | |
H5A | 1.2513 | 0.4075 | 0.0348 | 0.071* | |
C6 | 0.9068 (8) | 0.3894 (6) | 0.0450 (4) | 0.0425 (12) | |
C7 | 0.8786 (9) | 0.2528 (7) | −0.0268 (4) | 0.0503 (14) | |
H7A | 1.0094 | 0.1943 | −0.0651 | 0.060* | |
N8 | 0.6816 (8) | 0.2106 (6) | −0.0390 (3) | 0.0518 (12) | |
C9 | 0.4190 (9) | 0.9453 (7) | 0.3325 (4) | 0.0518 (13) | |
H9A | 0.5365 | 0.9745 | 0.3730 | 0.062* | |
C10 | 0.3728 (12) | 1.1032 (8) | 0.2631 (5) | 0.0772 (18) | |
H10A | 0.2751 | 1.0713 | 0.2143 | 0.093* | |
H10B | 0.5174 | 1.1431 | 0.2201 | 0.093* | |
C11 | 0.2537 (13) | 1.2501 (8) | 0.3345 (5) | 0.0802 (19) | |
H11A | 0.3449 | 1.2749 | 0.3875 | 0.096* | |
H11B | 0.2407 | 1.3560 | 0.2909 | 0.096* | |
C12 | 0.0161 (11) | 1.1958 (8) | 0.3911 (5) | 0.0682 (18) | |
H12A | −0.0468 | 1.2796 | 0.4462 | 0.082* | |
H12B | −0.0847 | 1.1991 | 0.3393 | 0.082* | |
C13 | 0.0174 (9) | 1.0143 (7) | 0.4429 (4) | 0.0486 (14) | |
C14 | −0.1721 (10) | 0.9610 (9) | 0.5196 (5) | 0.0620 (16) | |
H14A | −0.2950 | 1.0410 | 0.5406 | 0.074* | |
C15 | −0.1846 (11) | 0.7955 (9) | 0.5651 (5) | 0.0749 (18) | |
H15A | −0.3143 | 0.7635 | 0.6159 | 0.090* | |
C16 | −0.0009 (13) | 0.6756 (9) | 0.5347 (6) | 0.080 (2) | |
H16A | −0.0068 | 0.5621 | 0.5644 | 0.095* | |
C17 | 0.1892 (11) | 0.7268 (8) | 0.4602 (5) | 0.0665 (16) | |
H17A | 0.3134 | 0.6471 | 0.4414 | 0.080* | |
C18 | 0.2020 (8) | 0.8935 (7) | 0.4123 (4) | 0.0465 (12) | |
C19 | 0.6721 (9) | 0.0655 (6) | −0.1121 (4) | 0.0498 (13) | |
H19A | 0.8294 | 0.0400 | −0.1523 | 0.060* | |
C20 | 0.5911 (13) | −0.0955 (8) | −0.0465 (5) | 0.0728 (17) | |
H20A | 0.4515 | −0.0668 | 0.0058 | 0.087* | |
H20B | 0.7086 | −0.1390 | −0.0075 | 0.087* | |
C21 | 0.5425 (13) | −0.2380 (8) | −0.1206 (5) | 0.0755 (19) | |
H21A | 0.6802 | −0.2628 | −0.1750 | 0.091* | |
H21B | 0.5024 | −0.3453 | −0.0786 | 0.091* | |
C22 | 0.3465 (11) | −0.1769 (9) | −0.1746 (5) | 0.0688 (18) | |
H22A | 0.3350 | −0.2584 | −0.2300 | 0.083* | |
H22B | 0.2028 | −0.1782 | −0.1216 | 0.083* | |
C23 | 0.3768 (9) | 0.0051 (8) | −0.2248 (4) | 0.0503 (14) | |
C24 | 0.2515 (10) | 0.0601 (9) | −0.3022 (4) | 0.0624 (15) | |
H24A | 0.1532 | −0.0175 | −0.3233 | 0.075* | |
C25 | 0.2684 (12) | 0.2252 (10) | −0.3484 (5) | 0.079 (2) | |
H25A | 0.1830 | 0.2591 | −0.4004 | 0.095* | |
C26 | 0.4143 (14) | 0.3418 (9) | −0.3167 (6) | 0.086 (2) | |
H26A | 0.4269 | 0.4550 | −0.3469 | 0.103* | |
C27 | 0.5398 (11) | 0.2877 (8) | −0.2403 (5) | 0.0671 (17) | |
H27A | 0.6391 | 0.3653 | −0.2199 | 0.080* | |
C28 | 0.5226 (8) | 0.1213 (7) | −0.1928 (4) | 0.0484 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0351 (7) | 0.0574 (8) | 0.0551 (7) | −0.0009 (5) | −0.0088 (5) | −0.0201 (6) |
N1 | 0.045 (3) | 0.058 (3) | 0.049 (3) | 0.004 (2) | −0.006 (2) | −0.026 (2) |
C2 | 0.049 (3) | 0.055 (3) | 0.047 (3) | −0.007 (3) | −0.013 (2) | −0.016 (3) |
C3 | 0.039 (3) | 0.058 (3) | 0.048 (3) | −0.002 (2) | −0.016 (2) | −0.014 (3) |
C4 | 0.036 (3) | 0.071 (4) | 0.070 (4) | 0.000 (3) | −0.017 (3) | −0.027 (3) |
C5 | 0.033 (3) | 0.075 (4) | 0.072 (4) | 0.005 (3) | −0.010 (2) | −0.031 (3) |
C6 | 0.031 (3) | 0.050 (3) | 0.046 (3) | 0.004 (2) | −0.006 (2) | −0.011 (2) |
C7 | 0.046 (3) | 0.057 (3) | 0.048 (3) | 0.010 (3) | −0.007 (2) | −0.018 (3) |
N8 | 0.048 (3) | 0.059 (3) | 0.050 (3) | −0.003 (2) | −0.008 (2) | −0.023 (2) |
C9 | 0.049 (3) | 0.053 (3) | 0.054 (3) | −0.001 (3) | −0.009 (3) | −0.022 (3) |
C10 | 0.102 (5) | 0.061 (4) | 0.060 (4) | −0.002 (3) | 0.005 (3) | −0.015 (3) |
C11 | 0.109 (5) | 0.050 (4) | 0.070 (4) | 0.005 (3) | 0.010 (4) | −0.007 (3) |
C12 | 0.082 (5) | 0.062 (4) | 0.060 (4) | 0.024 (3) | −0.015 (3) | −0.022 (3) |
C13 | 0.048 (3) | 0.057 (3) | 0.043 (3) | 0.002 (3) | −0.012 (3) | −0.016 (3) |
C14 | 0.056 (3) | 0.075 (4) | 0.056 (3) | 0.009 (3) | −0.009 (3) | −0.027 (3) |
C15 | 0.075 (4) | 0.082 (5) | 0.062 (4) | −0.011 (4) | 0.006 (3) | −0.022 (4) |
C16 | 0.104 (5) | 0.061 (4) | 0.066 (4) | −0.012 (4) | 0.001 (4) | −0.002 (4) |
C17 | 0.072 (4) | 0.059 (4) | 0.064 (4) | 0.007 (3) | −0.003 (3) | −0.011 (3) |
C18 | 0.045 (3) | 0.054 (3) | 0.043 (3) | 0.001 (3) | −0.012 (2) | −0.019 (3) |
C19 | 0.052 (3) | 0.053 (3) | 0.044 (3) | 0.000 (3) | −0.007 (2) | −0.017 (3) |
C20 | 0.114 (5) | 0.060 (4) | 0.051 (3) | −0.010 (4) | −0.030 (3) | −0.011 (3) |
C21 | 0.119 (5) | 0.055 (4) | 0.056 (4) | −0.012 (4) | −0.021 (4) | −0.009 (3) |
C22 | 0.074 (4) | 0.078 (5) | 0.056 (4) | −0.028 (4) | −0.008 (3) | −0.017 (3) |
C23 | 0.048 (3) | 0.057 (3) | 0.043 (3) | −0.007 (3) | 0.001 (3) | −0.019 (3) |
C24 | 0.056 (3) | 0.079 (4) | 0.054 (3) | 0.003 (3) | −0.013 (3) | −0.028 (3) |
C25 | 0.096 (5) | 0.084 (5) | 0.066 (4) | 0.026 (4) | −0.037 (4) | −0.028 (4) |
C26 | 0.129 (6) | 0.057 (4) | 0.080 (5) | 0.016 (4) | −0.044 (5) | −0.010 (4) |
C27 | 0.084 (4) | 0.059 (4) | 0.064 (4) | −0.003 (3) | −0.022 (4) | −0.019 (3) |
C28 | 0.050 (3) | 0.046 (3) | 0.049 (3) | 0.006 (2) | −0.006 (2) | −0.018 (3) |
S1—C6 | 1.724 (5) | C14—H14A | 0.9300 |
S1—C3 | 1.728 (5) | C15—C16 | 1.390 (9) |
N1—C2 | 1.255 (6) | C15—H15A | 0.9300 |
N1—C9 | 1.471 (6) | C16—C17 | 1.373 (9) |
C2—C3 | 1.458 (7) | C16—H16A | 0.9300 |
C2—H2A | 0.9300 | C17—C18 | 1.386 (8) |
C3—C4 | 1.348 (7) | C17—H17A | 0.9300 |
C4—C5 | 1.420 (7) | C19—C20 | 1.496 (7) |
C4—H4A | 0.9300 | C19—C28 | 1.518 (7) |
C5—C6 | 1.355 (6) | C19—H19A | 0.9800 |
C5—H5A | 0.9300 | C20—C21 | 1.536 (8) |
C6—C7 | 1.445 (7) | C20—H20A | 0.9700 |
C7—N8 | 1.263 (6) | C20—H20B | 0.9700 |
C7—H7A | 0.9300 | C21—C22 | 1.508 (9) |
N8—C19 | 1.479 (6) | C21—H21A | 0.9700 |
C9—C10 | 1.512 (8) | C21—H21B | 0.9700 |
C9—C18 | 1.520 (7) | C22—C23 | 1.507 (9) |
C9—H9A | 0.9800 | C22—H22A | 0.9700 |
C10—C11 | 1.522 (8) | C22—H22B | 0.9700 |
C10—H10A | 0.9700 | C23—C24 | 1.384 (8) |
C10—H10B | 0.9700 | C23—C28 | 1.389 (7) |
C11—C12 | 1.510 (9) | C24—C25 | 1.367 (9) |
C11—H11A | 0.9700 | C24—H24A | 0.9300 |
C11—H11B | 0.9700 | C25—C26 | 1.390 (10) |
C12—C13 | 1.509 (8) | C25—H25A | 0.9300 |
C12—H12A | 0.9700 | C26—C27 | 1.374 (8) |
C12—H12B | 0.9700 | C26—H26A | 0.9300 |
C13—C14 | 1.390 (8) | C27—C28 | 1.382 (7) |
C13—C18 | 1.398 (7) | C27—H27A | 0.9300 |
C14—C15 | 1.366 (9) | ||
C6—S1—C3 | 91.5 (2) | C16—C15—H15A | 120.4 |
C2—N1—C9 | 116.5 (4) | C17—C16—C15 | 119.2 (7) |
N1—C2—C3 | 121.5 (5) | C17—C16—H16A | 120.4 |
N1—C2—H2A | 119.3 | C15—C16—H16A | 120.4 |
C3—C2—H2A | 119.3 | C16—C17—C18 | 122.1 (6) |
C4—C3—C2 | 129.7 (5) | C16—C17—H17A | 119.0 |
C4—C3—S1 | 111.3 (4) | C18—C17—H17A | 119.0 |
C2—C3—S1 | 119.1 (4) | C17—C18—C13 | 118.7 (5) |
C3—C4—C5 | 113.2 (5) | C17—C18—C9 | 120.0 (5) |
C3—C4—H4A | 123.4 | C13—C18—C9 | 121.2 (5) |
C5—C4—H4A | 123.4 | N8—C19—C20 | 109.4 (4) |
C6—C5—C4 | 112.6 (5) | N8—C19—C28 | 110.1 (4) |
C6—C5—H5A | 123.7 | C20—C19—C28 | 113.3 (4) |
C4—C5—H5A | 123.7 | N8—C19—H19A | 108.0 |
C5—C6—C7 | 129.0 (5) | C20—C19—H19A | 108.0 |
C5—C6—S1 | 111.4 (4) | C28—C19—H19A | 108.0 |
C7—C6—S1 | 119.6 (4) | C19—C20—C21 | 109.9 (4) |
N8—C7—C6 | 121.9 (5) | C19—C20—H20A | 109.7 |
N8—C7—H7A | 119.1 | C21—C20—H20A | 109.7 |
C6—C7—H7A | 119.1 | C19—C20—H20B | 109.7 |
C7—N8—C19 | 117.5 (4) | C21—C20—H20B | 109.7 |
N1—C9—C10 | 109.1 (4) | H20A—C20—H20B | 108.2 |
N1—C9—C18 | 110.3 (4) | C22—C21—C20 | 109.9 (5) |
C10—C9—C18 | 111.6 (5) | C22—C21—H21A | 109.7 |
N1—C9—H9A | 108.6 | C20—C21—H21A | 109.7 |
C10—C9—H9A | 108.6 | C22—C21—H21B | 109.7 |
C18—C9—H9A | 108.6 | C20—C21—H21B | 109.7 |
C9—C10—C11 | 109.6 (5) | H21A—C21—H21B | 108.2 |
C9—C10—H10A | 109.7 | C23—C22—C21 | 112.9 (5) |
C11—C10—H10A | 109.7 | C23—C22—H22A | 109.0 |
C9—C10—H10B | 109.7 | C21—C22—H22A | 109.0 |
C11—C10—H10B | 109.7 | C23—C22—H22B | 109.0 |
H10A—C10—H10B | 108.2 | C21—C22—H22B | 109.0 |
C12—C11—C10 | 109.6 (5) | H22A—C22—H22B | 107.8 |
C12—C11—H11A | 109.7 | C24—C23—C28 | 119.1 (5) |
C10—C11—H11A | 109.7 | C24—C23—C22 | 119.5 (5) |
C12—C11—H11B | 109.7 | C28—C23—C22 | 121.4 (5) |
C10—C11—H11B | 109.7 | C25—C24—C23 | 121.8 (6) |
H11A—C11—H11B | 108.2 | C25—C24—H24A | 119.1 |
C13—C12—C11 | 112.9 (5) | C23—C24—H24A | 119.1 |
C13—C12—H12A | 109.0 | C24—C25—C26 | 119.3 (6) |
C11—C12—H12A | 109.0 | C24—C25—H25A | 120.4 |
C13—C12—H12B | 109.0 | C26—C25—H25A | 120.4 |
C11—C12—H12B | 109.0 | C27—C26—C25 | 119.1 (6) |
H12A—C12—H12B | 107.8 | C27—C26—H26A | 120.4 |
C14—C13—C18 | 118.4 (5) | C25—C26—H26A | 120.4 |
C14—C13—C12 | 120.1 (5) | C26—C27—C28 | 121.9 (6) |
C18—C13—C12 | 121.5 (5) | C26—C27—H27A | 119.1 |
C15—C14—C13 | 122.5 (6) | C28—C27—H27A | 119.1 |
C15—C14—H14A | 118.8 | C27—C28—C23 | 118.8 (5) |
C13—C14—H14A | 118.8 | C27—C28—C19 | 119.8 (5) |
C14—C15—C16 | 119.1 (6) | C23—C28—C19 | 121.3 (5) |
C14—C15—H15A | 120.4 | ||
C9—N1—C2—C3 | −176.4 (5) | C12—C13—C18—C17 | −177.8 (5) |
N1—C2—C3—C4 | 172.4 (6) | C14—C13—C18—C9 | −177.3 (5) |
N1—C2—C3—S1 | −6.2 (7) | C12—C13—C18—C9 | 5.4 (7) |
C6—S1—C3—C4 | −1.4 (5) | N1—C9—C18—C17 | 39.8 (6) |
C6—S1—C3—C2 | 177.5 (4) | C10—C9—C18—C17 | 161.1 (5) |
C2—C3—C4—C5 | −177.8 (5) | N1—C9—C18—C13 | −143.5 (4) |
S1—C3—C4—C5 | 0.9 (6) | C10—C9—C18—C13 | −22.1 (6) |
C3—C4—C5—C6 | 0.2 (7) | C7—N8—C19—C20 | 105.5 (6) |
C4—C5—C6—C7 | 178.9 (5) | C7—N8—C19—C28 | −129.5 (5) |
C4—C5—C6—S1 | −1.3 (6) | N8—C19—C20—C21 | 170.8 (5) |
C3—S1—C6—C5 | 1.5 (4) | C28—C19—C20—C21 | 47.7 (7) |
C3—S1—C6—C7 | −178.7 (4) | C19—C20—C21—C22 | −64.0 (7) |
C5—C6—C7—N8 | −179.1 (6) | C20—C21—C22—C23 | 49.0 (7) |
S1—C6—C7—N8 | 1.1 (7) | C21—C22—C23—C24 | 161.6 (5) |
C6—C7—N8—C19 | −178.2 (5) | C21—C22—C23—C28 | −20.5 (8) |
C2—N1—C9—C10 | 102.3 (6) | C28—C23—C24—C25 | 0.4 (8) |
C2—N1—C9—C18 | −134.9 (5) | C22—C23—C24—C25 | 178.4 (6) |
N1—C9—C10—C11 | 173.7 (5) | C23—C24—C25—C26 | −0.3 (9) |
C18—C9—C10—C11 | 51.6 (7) | C24—C25—C26—C27 | 0.5 (10) |
C9—C10—C11—C12 | −66.2 (7) | C25—C26—C27—C28 | −0.9 (10) |
C10—C11—C12—C13 | 48.1 (7) | C26—C27—C28—C23 | 1.0 (8) |
C11—C12—C13—C14 | 164.1 (5) | C26—C27—C28—C19 | 177.5 (6) |
C11—C12—C13—C18 | −18.7 (8) | C24—C23—C28—C27 | −0.7 (7) |
C18—C13—C14—C15 | −0.5 (8) | C22—C23—C28—C27 | −178.7 (6) |
C12—C13—C14—C15 | 176.8 (5) | C24—C23—C28—C19 | −177.2 (5) |
C13—C14—C15—C16 | 0.5 (9) | C22—C23—C28—C19 | 4.9 (8) |
C14—C15—C16—C17 | 0.5 (10) | N8—C19—C28—C27 | 41.7 (6) |
C15—C16—C17—C18 | −1.6 (10) | C20—C19—C28—C27 | 164.5 (5) |
C16—C17—C18—C13 | 1.6 (9) | N8—C19—C28—C23 | −141.9 (5) |
C16—C17—C18—C9 | 178.4 (6) | C20—C19—C28—C23 | −19.1 (7) |
C14—C13—C18—C17 | −0.5 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···S1i | 0.93 | 3.00 | 3.562 (5) | 121 |
C5—H5A···S1i | 0.93 | 2.97 | 3.547 (5) | 122 |
Symmetry code: (i) x+1, y, z. |
C24H26N2O2S | Dx = 1.191 Mg m−3 |
Mr = 406.53 | Melting point: 405 K |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
a = 25.3917 (13) Å | Cell parameters from 2504 reflections |
b = 5.9488 (3) Å | θ = 3.0–24.2° |
c = 7.5623 (4) Å | µ = 0.16 mm−1 |
β = 97.174 (4)° | T = 298 K |
V = 1133.34 (10) Å3 | Prism, colourless |
Z = 2 | 0.45 × 0.33 × 0.12 mm |
F(000) = 432 |
Agilent Xcalibur (Atlas, Gemini) diffractometer | 2221 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1892 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ω scans | θmax = 26.1°, θmin = 3.0° |
Absorption correction: analytical (CrysAlis PRO; Agilent, 2013) | h = −31→31 |
Tmin = 0.973, Tmax = 0.993 | k = −7→7 |
6341 measured reflections | l = −9→9 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0393P)2 + 0.1801P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.085 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.11 e Å−3 |
2221 reflections | Δρmin = −0.17 e Å−3 |
134 parameters | Absolute structure: Flack x determined using 708 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
1 restraint | Absolute structure parameter: −0.02 (4) |
C24H26N2O2S | V = 1133.34 (10) Å3 |
Mr = 406.53 | Z = 2 |
Monoclinic, C2 | Mo Kα radiation |
a = 25.3917 (13) Å | µ = 0.16 mm−1 |
b = 5.9488 (3) Å | T = 298 K |
c = 7.5623 (4) Å | 0.45 × 0.33 × 0.12 mm |
β = 97.174 (4)° |
Agilent Xcalibur (Atlas, Gemini) diffractometer | 2221 independent reflections |
Absorption correction: analytical (CrysAlis PRO; Agilent, 2013) | 1892 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.993 | Rint = 0.027 |
6341 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.085 | Δρmax = 0.11 e Å−3 |
S = 1.02 | Δρmin = −0.17 e Å−3 |
2221 reflections | Absolute structure: Flack x determined using 708 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
134 parameters | Absolute structure parameter: −0.02 (4) |
1 restraint |
x | y | z | Uiso*/Ueq | ||
S1 | 0.5000 | 0.37429 (14) | 0.5000 | 0.0490 (3) | |
N1 | 0.56565 (9) | 0.3213 (4) | 0.1855 (3) | 0.0471 (6) | |
C2 | 0.55195 (11) | 0.5176 (5) | 0.2189 (4) | 0.0469 (7) | |
H2A | 0.5608 | 0.6324 | 0.1445 | 0.056* | |
C3 | 0.52314 (10) | 0.5774 (5) | 0.3665 (4) | 0.0449 (6) | |
C4 | 0.51313 (13) | 0.7856 (5) | 0.4229 (4) | 0.0596 (8) | |
H4A | 0.5225 | 0.9159 | 0.3665 | 0.072* | |
C5 | 0.59848 (11) | 0.2933 (4) | 0.0386 (4) | 0.0484 (7) | |
H5A | 0.5949 | 0.4291 | −0.0354 | 0.058* | |
C6 | 0.57863 (13) | 0.0963 (6) | −0.0754 (4) | 0.0658 (8) | |
H6A | 0.5416 | 0.1162 | −0.1164 | 0.099* | |
H6B | 0.5835 | −0.0394 | −0.0065 | 0.099* | |
H6C | 0.5981 | 0.0861 | −0.1759 | 0.099* | |
C7 | 0.65613 (11) | 0.2719 (4) | 0.1189 (3) | 0.0441 (6) | |
C8 | 0.69277 (11) | 0.4349 (4) | 0.0871 (4) | 0.0494 (7) | |
H8A | 0.6817 | 0.5585 | 0.0168 | 0.059* | |
C9 | 0.74515 (11) | 0.4171 (5) | 0.1576 (4) | 0.0571 (8) | |
H9A | 0.7692 | 0.5278 | 0.1343 | 0.069* | |
C10 | 0.76215 (11) | 0.2354 (6) | 0.2628 (4) | 0.0546 (7) | |
C11 | 0.72642 (12) | 0.0745 (6) | 0.2994 (4) | 0.0593 (8) | |
H11A | 0.7375 | −0.0469 | 0.3722 | 0.071* | |
C12 | 0.67374 (12) | 0.0936 (6) | 0.2275 (4) | 0.0551 (8) | |
H12A | 0.6497 | −0.0161 | 0.2528 | 0.066* | |
O1 | 0.81556 (9) | 0.2307 (5) | 0.3227 (3) | 0.0781 (7) | |
C13 | 0.83539 (15) | 0.0345 (9) | 0.4189 (5) | 0.1010 (15) | |
H13A | 0.8734 | 0.0434 | 0.4432 | 0.152* | |
H13B | 0.8257 | −0.0970 | 0.3487 | 0.152* | |
H13C | 0.8204 | 0.0258 | 0.5292 | 0.152* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0540 (6) | 0.0354 (5) | 0.0603 (6) | 0.000 | 0.0183 (4) | 0.000 |
N1 | 0.0442 (13) | 0.0512 (16) | 0.0477 (13) | 0.0014 (10) | 0.0129 (10) | 0.0058 (10) |
C2 | 0.0460 (15) | 0.0443 (18) | 0.0507 (16) | −0.0021 (13) | 0.0071 (13) | 0.0121 (13) |
C3 | 0.0421 (14) | 0.0392 (14) | 0.0534 (17) | −0.0002 (12) | 0.0062 (13) | 0.0052 (12) |
C4 | 0.074 (2) | 0.0365 (16) | 0.071 (2) | 0.0007 (13) | 0.0193 (16) | 0.0074 (13) |
C5 | 0.0497 (16) | 0.0537 (18) | 0.0434 (15) | 0.0015 (12) | 0.0120 (12) | 0.0097 (12) |
C6 | 0.0626 (19) | 0.079 (2) | 0.0551 (19) | −0.0010 (18) | 0.0058 (15) | −0.0036 (17) |
C7 | 0.0468 (15) | 0.0492 (15) | 0.0387 (14) | 0.0022 (13) | 0.0147 (12) | 0.0018 (12) |
C8 | 0.0559 (17) | 0.0500 (17) | 0.0451 (14) | −0.0025 (13) | 0.0169 (13) | 0.0045 (12) |
C9 | 0.0528 (17) | 0.067 (2) | 0.0548 (17) | −0.0139 (16) | 0.0177 (14) | −0.0004 (16) |
C10 | 0.0455 (16) | 0.078 (2) | 0.0414 (16) | 0.0001 (15) | 0.0080 (13) | −0.0080 (15) |
C11 | 0.0575 (18) | 0.068 (2) | 0.0524 (18) | 0.0087 (17) | 0.0086 (14) | 0.0150 (15) |
C12 | 0.0527 (17) | 0.0569 (17) | 0.0574 (19) | −0.0031 (14) | 0.0138 (14) | 0.0147 (15) |
O1 | 0.0478 (13) | 0.121 (2) | 0.0642 (14) | −0.0021 (14) | 0.0011 (10) | −0.0011 (14) |
C13 | 0.063 (2) | 0.161 (4) | 0.075 (3) | 0.022 (3) | −0.0086 (19) | 0.022 (3) |
S1—C3i | 1.724 (3) | C7—C12 | 1.381 (4) |
S1—C3 | 1.724 (3) | C7—C8 | 1.385 (3) |
N1—C2 | 1.253 (3) | C8—C9 | 1.374 (4) |
N1—C5 | 1.480 (3) | C8—H8A | 0.9300 |
C2—C3 | 1.453 (4) | C9—C10 | 1.379 (4) |
C2—H2A | 0.9300 | C9—H9A | 0.9300 |
C3—C4 | 1.345 (4) | C10—C11 | 1.371 (4) |
C4—C4i | 1.413 (6) | C10—O1 | 1.375 (3) |
C4—H4A | 0.9300 | C11—C12 | 1.384 (4) |
C5—C6 | 1.504 (4) | C11—H11A | 0.9300 |
C5—C7 | 1.519 (4) | C12—H12A | 0.9300 |
C5—H5A | 0.9800 | O1—C13 | 1.433 (5) |
C6—H6A | 0.9600 | C13—H13A | 0.9600 |
C6—H6B | 0.9600 | C13—H13B | 0.9600 |
C6—H6C | 0.9600 | C13—H13C | 0.9600 |
C3i—S1—C3 | 91.01 (19) | C12—C7—C5 | 121.8 (2) |
C2—N1—C5 | 116.9 (2) | C8—C7—C5 | 120.4 (2) |
N1—C2—C3 | 124.2 (3) | C9—C8—C7 | 121.2 (3) |
N1—C2—H2A | 117.9 | C9—C8—H8A | 119.4 |
C3—C2—H2A | 117.9 | C7—C8—H8A | 119.4 |
C4—C3—C2 | 127.1 (3) | C8—C9—C10 | 120.1 (3) |
C4—C3—S1 | 111.6 (2) | C8—C9—H9A | 119.9 |
C2—C3—S1 | 121.3 (2) | C10—C9—H9A | 119.9 |
C3—C4—C4i | 112.91 (17) | C11—C10—O1 | 124.7 (3) |
C3—C4—H4A | 123.5 | C11—C10—C9 | 119.8 (3) |
C4i—C4—H4A | 123.5 | O1—C10—C9 | 115.5 (3) |
N1—C5—C6 | 109.7 (2) | C10—C11—C12 | 119.7 (3) |
N1—C5—C7 | 108.3 (2) | C10—C11—H11A | 120.2 |
C6—C5—C7 | 113.7 (2) | C12—C11—H11A | 120.2 |
N1—C5—H5A | 108.3 | C7—C12—C11 | 121.5 (3) |
C6—C5—H5A | 108.3 | C7—C12—H12A | 119.3 |
C7—C5—H5A | 108.3 | C11—C12—H12A | 119.3 |
C5—C6—H6A | 109.5 | C10—O1—C13 | 117.0 (3) |
C5—C6—H6B | 109.5 | O1—C13—H13A | 109.5 |
H6A—C6—H6B | 109.5 | O1—C13—H13B | 109.5 |
C5—C6—H6C | 109.5 | H13A—C13—H13B | 109.5 |
H6A—C6—H6C | 109.5 | O1—C13—H13C | 109.5 |
H6B—C6—H6C | 109.5 | H13A—C13—H13C | 109.5 |
C12—C7—C8 | 117.8 (3) | H13B—C13—H13C | 109.5 |
C5—N1—C2—C3 | −175.3 (2) | C12—C7—C8—C9 | 1.5 (4) |
N1—C2—C3—C4 | 171.0 (3) | C5—C7—C8—C9 | −179.4 (3) |
N1—C2—C3—S1 | −5.7 (4) | C7—C8—C9—C10 | −0.3 (4) |
C3i—S1—C3—C4 | −0.22 (17) | C8—C9—C10—C11 | −1.1 (4) |
C3i—S1—C3—C2 | 176.9 (3) | C8—C9—C10—O1 | 178.3 (2) |
C2—C3—C4—C4i | −176.3 (3) | O1—C10—C11—C12 | −178.1 (3) |
S1—C3—C4—C4i | 0.6 (4) | C9—C10—C11—C12 | 1.2 (4) |
C2—N1—C5—C6 | −136.4 (3) | C8—C7—C12—C11 | −1.4 (4) |
C2—N1—C5—C7 | 99.0 (3) | C5—C7—C12—C11 | 179.6 (3) |
N1—C5—C7—C12 | 63.9 (3) | C10—C11—C12—C7 | 0.0 (5) |
C6—C5—C7—C12 | −58.3 (3) | C11—C10—O1—C13 | 4.8 (4) |
N1—C5—C7—C8 | −115.0 (3) | C9—C10—O1—C13 | −174.6 (3) |
C6—C5—C7—C8 | 122.7 (3) |
Symmetry code: (i) −x+1, y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···S1ii | 0.93 | 2.99 | 3.572 (3) | 122 |
Symmetry code: (ii) x, y+1, z. |
C22H20F2N2S | Dx = 1.260 Mg m−3 |
Mr = 382.46 | Melting point: 420 K |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
a = 21.1153 (16) Å | Cell parameters from 2744 reflections |
b = 7.7846 (6) Å | θ = 3.8–23.2° |
c = 6.1343 (5) Å | µ = 0.19 mm−1 |
V = 1008.32 (14) Å3 | T = 298 K |
Z = 2 | Prism, colourless |
F(000) = 400 | 0.89 × 0.47 × 0.33 mm |
Agilent Xcalibur (Atlas, Gemini) diffractometer | 2067 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1591 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
Detector resolution: 10.5564 pixels mm-1 | θmax = 26.4°, θmin = 3.8° |
ω scans | h = −26→26 |
Absorption correction: analytical CrysAlis PRO, (Agilent, 2013) | k = −9→9 |
Tmin = 0.904, Tmax = 0.958 | l = −7→7 |
12336 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0384P)2 + 0.0613P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2067 reflections | Δρmax = 0.15 e Å−3 |
124 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Absolute structure: Flack x determined using 518 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.07 (6) |
C22H20F2N2S | V = 1008.32 (14) Å3 |
Mr = 382.46 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 21.1153 (16) Å | µ = 0.19 mm−1 |
b = 7.7846 (6) Å | T = 298 K |
c = 6.1343 (5) Å | 0.89 × 0.47 × 0.33 mm |
Agilent Xcalibur (Atlas, Gemini) diffractometer | 2067 independent reflections |
Absorption correction: analytical CrysAlis PRO, (Agilent, 2013) | 1591 reflections with I > 2σ(I) |
Tmin = 0.904, Tmax = 0.958 | Rint = 0.058 |
12336 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.092 | Δρmax = 0.15 e Å−3 |
S = 1.06 | Δρmin = −0.25 e Å−3 |
2067 reflections | Absolute structure: Flack x determined using 518 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
124 parameters | Absolute structure parameter: 0.07 (6) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
S1 | 0.5000 | 0.0000 | 1.06817 (15) | 0.0479 (3) | |
F1 | 0.85802 (10) | 0.3203 (3) | 0.5731 (5) | 0.1163 (9) | |
N1 | 0.58698 (11) | 0.3119 (3) | 1.0120 (4) | 0.0498 (6) | |
C2 | 0.56853 (13) | 0.2830 (4) | 1.2046 (5) | 0.0479 (8) | |
H2A | 0.5795 | 0.3610 | 1.3130 | 0.057* | |
C3 | 0.53102 (13) | 0.1344 (4) | 1.2646 (4) | 0.0461 (8) | |
C4 | 0.51751 (14) | 0.0774 (4) | 1.4690 (4) | 0.0556 (8) | |
H4A | 0.5300 | 0.1342 | 1.5953 | 0.067* | |
C5 | 0.62513 (14) | 0.4679 (4) | 0.9770 (5) | 0.0568 (8) | |
H5A | 0.6336 | 0.5216 | 1.1185 | 0.068* | |
C6 | 0.58661 (16) | 0.5931 (5) | 0.8368 (7) | 0.0829 (12) | |
H6A | 0.5476 | 0.6200 | 0.9094 | 0.124* | |
H6B | 0.5777 | 0.5412 | 0.6983 | 0.124* | |
H6C | 0.6105 | 0.6967 | 0.8149 | 0.124* | |
C7 | 0.68777 (14) | 0.4223 (3) | 0.8702 (5) | 0.0462 (7) | |
C8 | 0.74419 (15) | 0.4799 (4) | 0.9563 (5) | 0.0577 (8) | |
H8A | 0.7436 | 0.5427 | 1.0852 | 0.069* | |
C9 | 0.80144 (15) | 0.4470 (4) | 0.8567 (7) | 0.0697 (10) | |
H9A | 0.8391 | 0.4873 | 0.9163 | 0.084* | |
C10 | 0.80134 (17) | 0.3551 (5) | 0.6707 (7) | 0.0689 (10) | |
C11 | 0.74733 (18) | 0.2932 (4) | 0.5777 (5) | 0.0654 (9) | |
H11A | 0.7489 | 0.2301 | 0.4491 | 0.078* | |
C12 | 0.69042 (15) | 0.3265 (4) | 0.6789 (5) | 0.0543 (8) | |
H12A | 0.6532 | 0.2843 | 0.6184 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0499 (6) | 0.0559 (6) | 0.0379 (5) | −0.0056 (6) | 0.000 | 0.000 |
F1 | 0.0687 (14) | 0.1167 (19) | 0.164 (2) | −0.0047 (14) | 0.0485 (15) | −0.030 (2) |
N1 | 0.0452 (14) | 0.0502 (15) | 0.0540 (16) | −0.0082 (12) | 0.0032 (11) | −0.0028 (11) |
C2 | 0.0405 (16) | 0.054 (2) | 0.0489 (18) | −0.0028 (15) | −0.0043 (14) | −0.0073 (16) |
C3 | 0.0388 (15) | 0.0544 (19) | 0.0452 (17) | −0.0011 (15) | −0.0013 (13) | −0.0024 (14) |
C4 | 0.056 (2) | 0.071 (2) | 0.0396 (15) | −0.0115 (15) | −0.0020 (13) | −0.0040 (14) |
C5 | 0.0545 (18) | 0.0513 (19) | 0.0647 (18) | −0.0104 (16) | 0.0112 (15) | −0.0111 (16) |
C6 | 0.065 (2) | 0.060 (2) | 0.123 (3) | 0.0111 (19) | 0.023 (2) | 0.016 (2) |
C7 | 0.0468 (17) | 0.0403 (15) | 0.0514 (17) | −0.0063 (14) | 0.0002 (14) | 0.0001 (13) |
C8 | 0.0576 (19) | 0.0492 (17) | 0.0662 (19) | −0.0090 (17) | 0.0002 (16) | −0.0104 (18) |
C9 | 0.047 (2) | 0.064 (2) | 0.099 (3) | −0.0114 (17) | −0.0023 (19) | −0.007 (2) |
C10 | 0.054 (2) | 0.058 (2) | 0.095 (3) | −0.0009 (18) | 0.021 (2) | 0.001 (2) |
C11 | 0.075 (2) | 0.063 (2) | 0.0577 (19) | 0.000 (2) | 0.011 (2) | −0.0053 (18) |
C12 | 0.0499 (18) | 0.0573 (19) | 0.0557 (18) | −0.0058 (17) | −0.0063 (16) | −0.0020 (16) |
S1—C3i | 1.725 (3) | C6—H6A | 0.9600 |
S1—C3 | 1.725 (3) | C6—H6B | 0.9600 |
F1—C10 | 1.365 (4) | C6—H6C | 0.9600 |
N1—C2 | 1.264 (4) | C7—C8 | 1.378 (4) |
N1—C5 | 1.473 (4) | C7—C12 | 1.392 (4) |
C2—C3 | 1.450 (4) | C8—C9 | 1.378 (4) |
C2—H2A | 0.9300 | C8—H8A | 0.9300 |
C3—C4 | 1.360 (4) | C9—C10 | 1.347 (5) |
C4—C4i | 1.414 (6) | C9—H9A | 0.9300 |
C4—H4A | 0.9300 | C10—C11 | 1.363 (5) |
C5—C7 | 1.518 (4) | C11—C12 | 1.377 (4) |
C5—C6 | 1.533 (5) | C11—H11A | 0.9300 |
C5—H5A | 0.9800 | C12—H12A | 0.9300 |
C3i—S1—C3 | 91.4 (2) | H6A—C6—H6C | 109.5 |
C2—N1—C5 | 116.8 (3) | H6B—C6—H6C | 109.5 |
N1—C2—C3 | 123.2 (3) | C8—C7—C12 | 117.6 (3) |
N1—C2—H2A | 118.4 | C8—C7—C5 | 120.8 (3) |
C3—C2—H2A | 118.4 | C12—C7—C5 | 121.6 (3) |
C4—C3—C2 | 127.5 (3) | C7—C8—C9 | 121.9 (3) |
C4—C3—S1 | 111.5 (2) | C7—C8—H8A | 119.1 |
C2—C3—S1 | 120.9 (2) | C9—C8—H8A | 119.1 |
C3—C4—C4i | 112.81 (18) | C10—C9—C8 | 118.2 (3) |
C3—C4—H4A | 123.6 | C10—C9—H9A | 120.9 |
C4i—C4—H4A | 123.6 | C8—C9—H9A | 120.9 |
N1—C5—C7 | 110.3 (2) | C9—C10—C11 | 122.9 (3) |
N1—C5—C6 | 108.4 (2) | C9—C10—F1 | 118.4 (3) |
C7—C5—C6 | 111.6 (2) | C11—C10—F1 | 118.7 (3) |
N1—C5—H5A | 108.8 | C10—C11—C12 | 118.4 (3) |
C7—C5—H5A | 108.8 | C10—C11—H11A | 120.8 |
C6—C5—H5A | 108.8 | C12—C11—H11A | 120.8 |
C5—C6—H6A | 109.5 | C11—C12—C7 | 121.1 (3) |
C5—C6—H6B | 109.5 | C11—C12—H12A | 119.5 |
H6A—C6—H6B | 109.5 | C7—C12—H12A | 119.5 |
C5—C6—H6C | 109.5 | ||
C5—N1—C2—C3 | −179.6 (2) | C6—C5—C7—C12 | −67.4 (4) |
N1—C2—C3—C4 | 168.6 (3) | C12—C7—C8—C9 | 1.0 (5) |
N1—C2—C3—S1 | −8.7 (4) | C5—C7—C8—C9 | −176.9 (3) |
C3i—S1—C3—C4 | −0.29 (16) | C7—C8—C9—C10 | −0.4 (5) |
C3i—S1—C3—C2 | 177.4 (3) | C8—C9—C10—C11 | −0.2 (5) |
C2—C3—C4—C4i | −176.7 (3) | C8—C9—C10—F1 | −179.1 (3) |
S1—C3—C4—C4i | 0.8 (4) | C9—C10—C11—C12 | 0.0 (6) |
C2—N1—C5—C7 | 124.5 (3) | F1—C10—C11—C12 | 179.0 (3) |
C2—N1—C5—C6 | −113.0 (3) | C10—C11—C12—C7 | 0.6 (5) |
N1—C5—C7—C8 | −129.0 (3) | C8—C7—C12—C11 | −1.1 (4) |
C6—C5—C7—C8 | 110.4 (3) | C5—C7—C12—C11 | 176.7 (3) |
N1—C5—C7—C12 | 53.2 (4) |
Symmetry code: (i) −x+1, −y, z. |
C22H20Cl2N2S | Dx = 1.276 Mg m−3 |
Mr = 415.36 | Melting point: 434 K |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
a = 21.893 (2) Å | Cell parameters from 2744 reflections |
b = 7.9212 (6) Å | θ = 3.7–21.5° |
c = 6.2315 (4) Å | µ = 0.41 mm−1 |
V = 1080.66 (15) Å3 | T = 298 K |
Z = 2 | Prism, colorless |
F(000) = 432 | 0.52 × 0.40 × 0.07 mm |
Agilent Xcalibur (Atlas, Gemini) diffractometer | 2743 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1534 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
Detector resolution: 10.5564 pixels mm-1 | θmax = 29.5°, θmin = 3.3° |
ω scans | h = −28→27 |
Absorption correction: multi-scan CrysAlis PRO, (Agilent, 2013) | k = −10→9 |
Tmin = 0.692, Tmax = 1.000 | l = −8→8 |
14195 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0483P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
2743 reflections | Δρmax = 0.13 e Å−3 |
124 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Absolute structure: Flack x determined using 465 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.10 (6) |
C22H20Cl2N2S | V = 1080.66 (15) Å3 |
Mr = 415.36 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 21.893 (2) Å | µ = 0.41 mm−1 |
b = 7.9212 (6) Å | T = 298 K |
c = 6.2315 (4) Å | 0.52 × 0.40 × 0.07 mm |
Agilent Xcalibur (Atlas, Gemini) diffractometer | 2743 independent reflections |
Absorption correction: multi-scan CrysAlis PRO, (Agilent, 2013) | 1534 reflections with I > 2σ(I) |
Tmin = 0.692, Tmax = 1.000 | Rint = 0.058 |
14195 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.117 | Δρmax = 0.13 e Å−3 |
S = 1.01 | Δρmin = −0.17 e Å−3 |
2743 reflections | Absolute structure: Flack x determined using 465 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
124 parameters | Absolute structure parameter: 0.10 (6) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
S1 | 0.5000 | 1.0000 | −0.13764 (18) | 0.0590 (4) | |
Cl1 | 0.15354 (6) | 0.67176 (16) | 0.4970 (2) | 0.1059 (5) | |
N1 | 0.41391 (14) | 0.6958 (3) | −0.0839 (5) | 0.0612 (8) | |
C2 | 0.43185 (16) | 0.7244 (4) | −0.2735 (6) | 0.0589 (10) | |
H2A | 0.4204 | 0.6496 | −0.3812 | 0.071* | |
C3 | 0.46969 (15) | 0.8689 (4) | −0.3311 (5) | 0.0544 (9) | |
C4 | 0.48309 (16) | 0.9247 (4) | −0.5338 (5) | 0.0640 (10) | |
H4A | 0.4711 | 0.8688 | −0.6581 | 0.077* | |
C5 | 0.37559 (18) | 0.5438 (4) | −0.0520 (7) | 0.0677 (11) | |
H5A | 0.3625 | 0.5021 | −0.1927 | 0.081* | |
C6 | 0.4148 (2) | 0.4087 (5) | 0.0553 (9) | 0.0986 (17) | |
H6A | 0.4484 | 0.3803 | −0.0369 | 0.148* | |
H6B | 0.3905 | 0.3098 | 0.0810 | 0.148* | |
H6C | 0.4302 | 0.4509 | 0.1892 | 0.148* | |
C7 | 0.31964 (17) | 0.5839 (4) | 0.0796 (5) | 0.0555 (9) | |
C8 | 0.26313 (19) | 0.5202 (5) | 0.0255 (7) | 0.0701 (10) | |
H8A | 0.2593 | 0.4575 | −0.0999 | 0.084* | |
C9 | 0.21198 (19) | 0.5464 (5) | 0.1512 (7) | 0.0735 (11) | |
H9A | 0.1744 | 0.5020 | 0.1109 | 0.088* | |
C10 | 0.21746 (18) | 0.6384 (5) | 0.3351 (6) | 0.0640 (10) | |
C11 | 0.2728 (2) | 0.7062 (5) | 0.3945 (6) | 0.0691 (10) | |
H11A | 0.2761 | 0.7692 | 0.5199 | 0.083* | |
C12 | 0.32346 (18) | 0.6802 (4) | 0.2665 (5) | 0.0623 (9) | |
H12A | 0.3607 | 0.7276 | 0.3056 | 0.075* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0694 (9) | 0.0596 (7) | 0.0482 (6) | −0.0040 (7) | 0.000 | 0.000 |
Cl1 | 0.0878 (9) | 0.1061 (9) | 0.1238 (10) | 0.0069 (7) | 0.0384 (8) | 0.0026 (9) |
N1 | 0.062 (2) | 0.0569 (18) | 0.0643 (19) | −0.0089 (15) | 0.0064 (15) | 0.0009 (14) |
C2 | 0.055 (2) | 0.060 (2) | 0.061 (2) | 0.0015 (17) | −0.0031 (19) | −0.0056 (18) |
C3 | 0.050 (2) | 0.060 (2) | 0.0523 (19) | 0.0004 (17) | −0.0008 (16) | −0.0008 (17) |
C4 | 0.063 (3) | 0.080 (2) | 0.0487 (18) | −0.0130 (18) | −0.0011 (17) | −0.0059 (17) |
C5 | 0.071 (3) | 0.057 (2) | 0.075 (2) | −0.0098 (18) | 0.015 (2) | −0.0050 (18) |
C6 | 0.085 (3) | 0.064 (2) | 0.147 (4) | 0.011 (2) | 0.040 (3) | 0.019 (3) |
C7 | 0.061 (2) | 0.0442 (17) | 0.061 (2) | −0.0052 (17) | −0.0039 (18) | 0.0020 (16) |
C8 | 0.073 (3) | 0.061 (2) | 0.076 (2) | −0.017 (2) | −0.002 (2) | −0.014 (2) |
C9 | 0.063 (3) | 0.067 (3) | 0.091 (3) | −0.0168 (19) | −0.003 (2) | −0.007 (2) |
C10 | 0.065 (3) | 0.056 (2) | 0.072 (2) | 0.0010 (19) | 0.007 (2) | 0.007 (2) |
C11 | 0.081 (3) | 0.068 (2) | 0.059 (2) | −0.002 (2) | −0.003 (2) | −0.0067 (18) |
C12 | 0.059 (2) | 0.065 (2) | 0.063 (2) | −0.004 (2) | −0.010 (2) | −0.002 (2) |
S1—C3 | 1.724 (3) | C6—H6A | 0.9600 |
S1—C3i | 1.724 (3) | C6—H6B | 0.9600 |
Cl1—C10 | 1.746 (4) | C6—H6C | 0.9600 |
N1—C2 | 1.265 (4) | C7—C8 | 1.378 (5) |
N1—C5 | 1.481 (4) | C7—C12 | 1.394 (4) |
C2—C3 | 1.458 (5) | C8—C9 | 1.382 (5) |
C2—H2A | 0.9300 | C8—H8A | 0.9300 |
C3—C4 | 1.370 (4) | C9—C10 | 1.363 (5) |
C4—C4i | 1.404 (7) | C9—H9A | 0.9300 |
C4—H4A | 0.9300 | C10—C11 | 1.376 (5) |
C5—C7 | 1.508 (5) | C11—C12 | 1.382 (5) |
C5—C6 | 1.527 (5) | C11—H11A | 0.9300 |
C5—H5A | 0.9800 | C12—H12A | 0.9300 |
C3—S1—C3i | 91.3 (2) | H6A—C6—H6C | 109.5 |
C2—N1—C5 | 116.6 (3) | H6B—C6—H6C | 109.5 |
N1—C2—C3 | 123.2 (3) | C8—C7—C12 | 117.3 (4) |
N1—C2—H2A | 118.4 | C8—C7—C5 | 121.3 (3) |
C3—C2—H2A | 118.4 | C12—C7—C5 | 121.4 (3) |
C4—C3—C2 | 127.0 (3) | C7—C8—C9 | 122.2 (4) |
C4—C3—S1 | 111.6 (3) | C7—C8—H8A | 118.9 |
C2—C3—S1 | 121.3 (2) | C9—C8—H8A | 118.9 |
C3—C4—C4i | 112.8 (2) | C10—C9—C8 | 119.0 (4) |
C3—C4—H4A | 123.6 | C10—C9—H9A | 120.5 |
C4i—C4—H4A | 123.6 | C8—C9—H9A | 120.5 |
N1—C5—C7 | 111.2 (3) | C9—C10—C11 | 120.8 (4) |
N1—C5—C6 | 108.1 (3) | C9—C10—Cl1 | 119.8 (3) |
C7—C5—C6 | 111.5 (3) | C11—C10—Cl1 | 119.4 (3) |
N1—C5—H5A | 108.7 | C10—C11—C12 | 119.5 (3) |
C7—C5—H5A | 108.7 | C10—C11—H11A | 120.2 |
C6—C5—H5A | 108.7 | C12—C11—H11A | 120.2 |
C5—C6—H6A | 109.5 | C11—C12—C7 | 121.0 (4) |
C5—C6—H6B | 109.5 | C11—C12—H12A | 119.5 |
H6A—C6—H6B | 109.5 | C7—C12—H12A | 119.5 |
C5—C6—H6C | 109.5 | ||
C5—N1—C2—C3 | 179.8 (3) | C6—C5—C7—C12 | 74.9 (4) |
N1—C2—C3—C4 | −168.8 (4) | C12—C7—C8—C9 | −1.2 (5) |
N1—C2—C3—S1 | 7.3 (5) | C5—C7—C8—C9 | 175.8 (3) |
C3i—S1—C3—C4 | 0.42 (19) | C7—C8—C9—C10 | 0.0 (6) |
C3i—S1—C3—C2 | −176.3 (4) | C8—C9—C10—C11 | 0.8 (6) |
C2—C3—C4—C4i | 175.3 (4) | C8—C9—C10—Cl1 | −179.6 (3) |
S1—C3—C4—C4i | −1.1 (5) | C9—C10—C11—C12 | −0.3 (6) |
C2—N1—C5—C7 | −132.2 (3) | Cl1—C10—C11—C12 | −179.9 (3) |
C2—N1—C5—C6 | 105.1 (4) | C10—C11—C12—C7 | −1.0 (6) |
N1—C5—C7—C8 | 137.3 (4) | C8—C7—C12—C11 | 1.7 (5) |
C6—C5—C7—C8 | −102.0 (4) | C5—C7—C12—C11 | −175.3 (3) |
N1—C5—C7—C12 | −45.8 (4) |
Symmetry code: (i) −x+1, −y+2, z. |
Compound | Contact | C—H | H···S | C···S | C—H···S |
(I) | C4—H4A···S1i | 0.93 | 3.00 | 3.562 (5) | 120.6 |
(I) | C5—H5A···S1i | 0.93 | 2.97 | 3.547 (5) | 121.6 |
(II) | C4—H4A···S1ii | 0.93 | 2.99 | 3.572 (3) | 122.3 |
(III) | C4—H4A···S1iii | 0.93 | 3.15 | 3.743 (3) | 123.6 |
(IV) | C4—H4A···S1iv | 0.93 | 3.23 | 3.828 (4) | 124.2 |
Symmetry codes: (i) x + 1, y, z; (ii) x, y + 1, z; (iii) x, y, z + 1; (iv) x, y, z − 1. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C26H26N2S | C24H26N2O2S | C22H20F2N2S | C22H20Cl2N2S |
Mr | 398.55 | 406.53 | 382.46 | 415.36 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2 | Orthorhombic, P21212 | Orthorhombic, P21212 |
Temperature (K) | 298 | 298 | 298 | 298 |
a, b, c (Å) | 5.9093 (4), 7.6258 (5), 12.6570 (8) | 25.3917 (13), 5.9488 (3), 7.5623 (4) | 21.1153 (16), 7.7846 (6), 6.1343 (5) | 21.893 (2), 7.9212 (6), 6.2315 (4) |
α, β, γ (°) | 87.802 (5), 78.329 (5), 87.427 (5) | 90, 97.174 (4), 90 | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 557.76 (6) | 1133.34 (10) | 1008.32 (14) | 1080.66 (15) |
Z | 1 | 2 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.16 | 0.16 | 0.19 | 0.41 |
Crystal size (mm) | 0.34 × 0.12 × 0.06 | 0.45 × 0.33 × 0.12 | 0.89 × 0.47 × 0.33 | 0.52 × 0.40 × 0.07 |
Data collection | ||||
Diffractometer | Agilent Xcalibur (Atlas, Gemini) | Agilent Xcalibur (Atlas, Gemini) | Agilent Xcalibur (Atlas, Gemini) | Agilent Xcalibur (Atlas, Gemini) |
Absorption correction | Analytical CrysAlis PRO, (Agilent, 2013) | Analytical (CrysAlis PRO; Agilent, 2013) | Analytical CrysAlis PRO, (Agilent, 2013) | Multi-scan CrysAlis PRO, (Agilent, 2013) |
Tmin, Tmax | 0.969, 0.992 | 0.973, 0.993 | 0.904, 0.958 | 0.692, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6689, 4036, 2958 | 6341, 2221, 1892 | 12336, 2067, 1591 | 14195, 2743, 1534 |
Rint | 0.040 | 0.027 | 0.058 | 0.058 |
(sin θ/λ)max (Å−1) | 0.618 | 0.618 | 0.625 | 0.692 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.127, 1.02 | 0.036, 0.085, 1.02 | 0.044, 0.092, 1.06 | 0.052, 0.117, 1.01 |
No. of reflections | 4036 | 2221 | 2067 | 2743 |
No. of parameters | 262 | 134 | 124 | 124 |
No. of restraints | 3 | 1 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.19 | 0.11, −0.17 | 0.15, −0.25 | 0.13, −0.17 |
Absolute structure | Flack x determined using 962 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) | Flack x determined using 708 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) | Flack x determined using 518 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) | Flack x determined using 465 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | −0.12 (7) | −0.02 (4) | 0.07 (6) | 0.10 (6) |
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), Mercury (Macrae et al., 2008).
Acknowledgements
Support from VIEP–UAP is acknowledged.
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