research communications
Structure and spectroscopic properties of N,S-coordinating 2-methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline methanol monosolvate
aDepartment of Chemistry, 1250 Grand Lake Road, Cape Breton University, Sydney, Nova Scotia, B1P 6L2, Canada, and bUniversity of Alberta, X-ray Crystallography Laboratory, Department of Chemistry, Edmonton, Alberta, T6G 2G2, Canada
*Correspondence e-mail: matthias_bierenstiel@cbu.ca
The reaction of pyrrole-2-carboxaldehyde and 2-(methylsulfanyl)aniline in refluxing methanol gave an olive-green residue in which yellow crystals of the title compound, C12H12N2S·CH3OH, were grown from slow evaporation of methanol at 263 K. In the crystal, hydrogen-bonding interactions link the aniline molecule and a nearby methanol solvent molecule. These units are linked by a pair of weak C—H⋯Omethanol interactions, forming inversion dimers consisting of two main molecules and two solvent molecules.
Keywords: crystal structure; imine; Schiff base; hydrogen bonding; N,S-ligand.
CCDC reference: 1417853
1. Chemical context
Compounds that contain N- and S-donor atoms have exhibited biomedical activities such as antibacterial properties. In addition, such N,S-compounds can be useful ligands to form transition metal complexes which we have been investigating for their use as biomimetic models for Cu enzyme models (Alberto et al., 2013; Cross et al., 2011). Recently, we have reported the synthesis and structure of xylylene-bridged bis-[ortho-aminothiophenols] for the design of binuclear transition metal complexes (Alberto et al., 2013; Cross et al., 2011). Copper complexes of these N2S2-ligands are studied as small biomimetic metal models for the analysis of non-blue/type-II copper enzymes such as peptidylglycine α-hydroxylating monooxygenase (PHM), which is one of the two non-coupled copper ion domains of the bifunctional peptidylglycine α-amidating monooxygenase (PAM, EC 1.14.17.3) (Klinman, 2006; McIntyre et al., 2009). Recently, we reported the X-ray structure of a trinuclear palladium(II) complex containing N,S-coordinating 2-(benzylsulfanyl)anilinide and 1,3-benzothioazole-2-thiolate ligands (Cross et al., 2014). The 2-aminothiophenol group can be used as a synthetic building motif for the preparation of benzothiazolines (Chou et al., 2008), thioethers (Ham et al., 2006; Schwindt et al., 1976a) and polyurethanes (Schwindt et al., 1976b), and has medical applications in antitrypanosomal, antileishmanial and antimalarial treatments (Parveen et al., 2005).
Herein, we report the X-ray structure of 2-methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline methanol monosolvate (1) which features an aryl methyl thioether group and an imino-2-pyrrole motif. The imine pendant prevents the reversible formation of the benzothiazoline, a transformation that was evident in the structure we reported previously that featured a free amino group and was bonded to a palladium centre (Setifi et al., 2014). Li and co-workers first described the synthesis of (1) in 16% isolated yield (He et al., 2009). The 1H and 13C NMR data were reported and are congruent with our data (Basuli et al., 1996). Compound (1) was complexed with CrCl3(thf)3 (He et al., 2009) and with VCl3(thf)3 (Mu et al., 2011) as ethylene polymerization catalysts (He et al., 2009). We now provide additional compound data such as HRMS, UV–vis and FT–IR.
2. Structural commentary
Fig. 1 shows the molecular structure of the yellow title compound. The imino group is coplanar with the pyrrole group, and the dihedral angle between the plane of the combined (pyrrol-2-yl)imino moiety and that of the benzene ring carbons is 42.71 (5)°. The imino group N1–C8 bond distance [1.2829 (17) Å] is normal. The sulfur and imino nitrogen atoms are very nearly coplanar with the benzene ring atoms [S is 0.0595 (18) Å and N1 is 0.0620 (19) Å out of plane], while the methyl carbon C7 is 0.310 (3) Å out of the benzene ring plane.
The three heteroatoms of the main molecule of (1) are each involved in hydrogen-bonding interactions with the adjacent co-crystallized solvent methanol molecule (Fig. 2 and Table 1). The closest interaction is between the protonated nitrogen of the pyrrol-2-yl group and the methanol oxygen [N2⋯O1S = 2.9030 (16) Å; H2N⋯O1S = 2.025 (18) Å]. The methanol hydroxyl group shows somewhat weaker interactions with the imino nitrogen [N1⋯H1SO = 2.49 (2) Å; N1⋯O1S = 3.1116 (16) Å] and the sulfur atom [S1⋯H1SO = 2.76 (3) Å; S⋯O1S = 3.5134 (12) Å].
3. Supramolecular features
As shown in Fig. 3, the methanol molecules are sandwiched between the main molecules of (1) in such a manner as to preclude π–π stacking interactions between aromatic rings of adjacent molecules. The hydrogen-bonded methanol–main molecule units are linked by pairs of weakC—H⋯Omethanol interactions, forming inversion dimers consisting of two main molecules and two solvent molecules (Table 1).
In summary, 2-methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline is a conjugated imine that exhibits three hydrogen-bonding interactions to methanol within the crystal packing which would make the compound effective for tridentate N,N,S metal particularly in the case where the N-hydrogen of the pyrrol-2-yl group is deprotonated to form an anionic species.
4. Thioether bonding in related structures
This is the first crystallographic report of an NNS ligand system found in 2-methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline. The closest related structure to (1) is the reported molecular structure of 3-(imino-N-2-methylsulfanylphenyl)imidazo[1,5-a]pyridinium-1-thiolate (Patra et al., 2011a), where the imine-carbon atom is α to a nitrogen heteroatom and crystallizes in P. Related NNS-type ligands are published with their respective metal complexes.
A closely related compound that features a pyridyl group instead of a pyrrole has been extensively reported in metal complexes and whether the thioether bonds to the metal centre varies, which sheds perspective on the binding nature of compound (1). For example, the thioether of the pyridyl ligand does not initially bind to the metal centre of a manganese carbonyl complex unless in the presence of oxygen (Lumsden et al., 2014). When reacted with a rhenium carbonyl complex (Jana et al., 2013), the thioether does not participate in bonding, and in contrast, the thioether binds to iron in its respective carbonyl complex (Muthiah et al., 2015).
This variance in thioether bonding is also found when reacting the pyridyl ligand with various copper complexes (Addison et al., 1984; Schnödt et al., 2011; Patra et al., 2011b; Chatterjee et al., 2012; Balamurugan et al., 2006) where copper is our target metal centre for (1) and for our other NNS ligands. Addison and co-workers have reported a systematic study on the properties of various copper–thioether interactions (Addison et al., 1984). In the study, they considered the presence of a nitrogen donor in an equatorial plane to the thioether, strong donor solvents, and the redox chemistry of the resultant metal complexes, which would affect the displacement of the thioether group.
The methanol molecule present in the X-ray structure of (1) does illustrate the three heteroatoms that could bond to a metal centre, though perspective can be gained from the metal complexes formed with the pyridyl ligand relative. The reported molecular structures with the pyridyl metal complexes all feature distorted octahedral geometry. In the case of (1), the thioether group sits above the neighbouring benzene ring, which would contribute to the formation of a distorted octahedral complex and remove the direct equatorial interaction of the sulfur to the donating nitrogen of the imine group. In addition, the pyrrole substituent is relatively less basic than pyridine, hence deprotonation of the pyrrole ligand must occur to elicit coordination of a metal centre.
5. Synthesis and crystallization
All chemicals were purchased from commercial sources (Fisher Scientific and Sigma–Aldrich) and used without further purification. A colorless solution containing 0.683 g (7.18 mmol) of 2-pyrrolecarboxaldehyde dissolved in 15 mL of MeOH was added drop-wise to a light-green solution containing 1.00 g (7.18 mmol) of 2-(methylsulfanyl)aniline in 5 mL of MeOH with stirring. After refluxing the light-green solution overnight, the solution changed color to olive green. The solution was cooled to ambient temperature, and the solvent was removed under reduced pressure. The olive-green residue was dissolved in 10 mL of MeOH, and was placed in the freezer at 263 K with a needle-punctured rubber septum. Crystals formed from the solution, and, after several days, were collected by vacuum filtration and washed with cold hexanes. 0.780 g (50%) of yellow crystals were isolated.
6. Spectroscopic investigations
NMR spectra were recorded on a Bruker Avance II 400 MHz spectrometer operating at 400.17 MHz for 1H and 100.6 MHz for 13C, and were referenced to tetramethylsilane (δ = 0 p.p.m.). High-resolution MS data were obtained using a Waters XevoG2 QToF instrument in positive electrospray ionization mode. Theoretical m/z values are reported for an abundance greater than 10% of base signal. UV-Vis spectra were recorded in quartz cuvettes on a Varian Cary 100 Bio UV–Vis spectrometer. FT–IR spectra were recorded on a Thermo Nicolet 6700 FT–IR Spectrometer as KBr pellet (approximately 1.5 mg compound in 300 mg anhydrous KBr) in the 4,000 cm−1 to 400 cm−1 range with 2 cm−1 resolution.
Spectroscopic measurements confirmed the structure of (1). High-resolution gave an [M]+ ion of 217.0833 m/z, close to the calculated mass of 217.0755 m/z and the IR spectrum of (1) exhibited an imine stretch of 1611 cm−1 that is characteristic for aniline-based Absorbances located at 290 nm and 300 nm in the UV spectrum are characteristic of the π–π* transition of pyrrole and C=N bonds, respectively. The π–π* transition of benzene is also present with an absorbance around 350 nm.
1H NMR (400 MHz, CDCl3) δ = 9.63 (bs, 1H), 8.22 (s, 1H), 7.22–7.14 (m, 3H), 7.03 (bs, 1H), 6.99 (d, J = 7.6 Hz, 1H), 6.71 (dd, J = 1.2, 3.6 Hz, 1H), 6.34 (t, J = 2.8 Hz, 1H), 2.47 (s, 3H) p.p.m.13C{1H} NMR (100 MHz, CDCl3) δ = 149.1, 148.9, 133.9, 131.0, 125.9, 125.2, 124.3, 123.0, 117.5, 116.4, 110.6, 14.7 p.p.m. FT–IR (KBr) 3264, 3154, 2934, 3127, 3109. 3079, 3060, 2980, 2968, 2912, 2890, 2854, 1611, 1573, 1568, 1550, 1470, 1450, 1439, 1418, 1333, 1308, 1267, 1246, 1205, 1133, 1094, 1070, 1038, 975, 970, 956, 927, 882, 864, 844, 829, 781, 746, 725, 678, 603, 586 cm−1. HRMS (ESI–TOF) m/z: [M]+ Calculated for C12H12N2S 217.0755; found 217.0833. λmax/nm (DMF, 0.022 mg mL−1) 303 (λ/dm3 mol−1cm−1 21700), 270 (19100), 208 (sh).
7. details
Crystal data, data collection and structure . Hydrogen atoms attached to carbons were assigned positions based on the sp2 or sp3 geometries of their attached atoms. Hydrogens attached to sp2-hybridized carbons were given isotropic displacement parameters Uiso(H) = 1.2Uiso(C) for their attached atoms, while methyl-group hydrogens were given isotropic displacement parameters Uiso(H) = 1.5Ueq(C) for their attached carbons. The coordinates and displacement parameters for the hydrogens attached to N2 and O1S were allowed to refine freely.
details are summarized in Table 2Supporting information
CCDC reference: 1417853
10.1107/S205698901501590X/bg2566sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S205698901501590X/bg2566Isup2.hkl
Supporting information file. DOI: 10.1107/S205698901501590X/bg2566Isup3.cml
Compounds that contain N- and S-donor atoms have exhibited biomedical activities such as antibacterial properties. In addition, such N,S-compounds can be useful ligands to form transition metal complexes which we have been investigating for their use as biomimetic models for Cu enzyme models (Alberto et al., 2013; Cross et al., 2011). Recently, we have reported the synthesis and structure of xylylene-bridged bis-[ortho-aminothiophenols] for the design of binuclear transition metal complexes (Alberto et al., 2013; Cross et al., 2011). Copper complexes of these N2S2-ligands are studied as small biomimetic metal models for the analysis of non-blue/type-II copper enzymes such as peptidylglycine α-hydroxylating monooxygenase (PHM), which is one of the two non-coupled copper ion domains of the bifunctional peptidylglycine α-amidating monooxygenase (PAM, EC 1.14.17.3) (Klinman, 2006; McIntyre et al., 2009). Recently, we reported the X-ray structure of a trinuclear palladium(II) complex containing N,S-coordinating 2-(benzylsulfanyl)anilinide and 1,3-benzothioazole-2-thiolate ligands (Cross et al., 2014). The 2-aminothiophenol group can be used as a synthetic building motif for the preparation of benzothiazolines (Chou et al., 2008), thioethers (Ham et al., 2006; Schwindt et al., 1976a) and polyurethanes (Schwindt et al., 1976b), and has medical applications in antitrypanosomal, antileishmanial and antimalarial treatments (Parveen et al., 2005).
Herein, we report the X-ray structure of 2-methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline methanol monosolvate (1) which features an aryl methyl thioether group and an imino-2-pyrrole motif. The imine pendant prevents the reversible formation of the benzothiazoline, a transformation that was evident in the structure we reported previously that featured a free amino group and was bonded to a palladium centre (Setifi et al., 2014). Li and co-workers first described the synthesis of (1) in 16% isolated yield (He et al., 2009). The 1H and 13C NMR data were reported and are congruent with our data (Basuli et al., 1996). Compound (1) was complexed with CrCl3(thf)3 (He et al., 2009) and with VCl3(thf)3 (Mu et al., 2011) as ethylene polymerization catalysts (He et al., 2009). We now provide additional compound data such as HRMS, UV–vis and FT–IR.
Fig. 1 shows the molecular structure of this yellow compound. The imino group is coplanar with the pyrrole group, and the dihedral angle between the plane of the combined (pyrrol-2-yl)imino moiety and that of the benzene ring carbons is 42.71 (5)°. The imino group N1–C8 bond distance [1.2829 (17) Å] is normal. The sulfur and imino nitrogen atoms are very nearly coplanar with the benzene ring atoms [S is 0.0595 (18) Å and N1 is 0.0620 (19) Å out of plane], while the methyl carbon C7 is 0.310 (3) Å out of the benzene ring plane.
As shown in Fig. 2, the three heteroatoms of the main molecule of (1) are each involved in hydrogen-bonding interactions with the adjacent co-crystallized solvent methanol molecule. The closest interaction is between the protonated nitrogen of the pyrrol-2-yl group and the methanol oxygen [N2···O1S = 2.9030 (16) Å; H2N···O1S = 2.025 (18) Å]. The methanol hydroxyl group shows somewhat weaker interactions with the imino nitrogen [N1···H1SO = 2.49 (2) Å; N1···O1S = 3.1116 (16) Å] and the sulfur atom [S1···H1SO = 2.76 (3) Å; S···O1S = 3.5134 (12) Å].
Table 1 provides information on hydrogen-bonding interactions and Fig. 3 illustrates the crystal packing as viewed roughly along the a axis of the π–π stacking interactions between aromatic rings of adjacent molecules. Weak intermolecular C—H···X interactions are observed: C7—H7B···O1S(-x, 1 - y, -z) = 2.55 Å.
The methanol molecules are sandwiched between the main molecules of (1) in such a manner as to precludeIn summary, 2-methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline is a conjugated imine that exhibits three hydrogen-bonding interactions to methanol within the crystal packing which would make the compound effective for tridentate N,N,S metal
particularly in the case where the N-hydrogen of the pyrrol-2-yl group is deprotonated to form an anionic species.This is the first crystallographic report of an NNS ligand system found in 2-methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline. The closest related structure to (1) is the reported molecular structure of 3-(imino-N-2- methylsulfanylphenyl)imidazo[1,5-a]pyridinium-1-thiolate (Patra et al., 2011a), where the imine-carbon atom is α to a nitrogen heteroatom and crystallizes in P1. Related NNS-type ligands are published with their respective metal complexes.
A closely related compound that features a pyridyl group instead of a pyrrole has been extensively reported in metal complexes and whether the thioether bonds to the metal centre varies, which sheds perspective on the binding nature of compound (1). For example, the thioether of the pyridyl ligand does not initially bind to the metal centre of a manganese carbonyl complex unless in the presence of oxygen (Lumsden et al., 2014). When reacted with a rhenium carbonyl complex (Jana et al., 2013), the thioether does not participate in bonding, and in contrast, the thioether binds to iron in its respective carbonyl complex (Muthiah et al., 2015).
This variance in thioether bonding is also found when reacting the pyridyl ligand with various copper complexes (Addison et al., 1984; Schnödt et al., 2011; Patra et al., 2011b; Chatterjee et al., 2012; Balamurugan et al., 2006) where copper is our target metal centre for (1) and for our other NNS ligands. Addison and co-workers have reported a systematic study on the properties of various copper–thioether interactions (Addison et al., 1984). In the study, they considered the presence of a nitrogen donor in an equatorial plane to the thioether, strong donor solvents, and the redox chemistry of the resultant metal complexes, which would affect the displacement of the thioether group.
The methanol molecule present in the X-ray structure of (1) does illustrate the three heteroatoms that could bond to a metal centre, though perspective can be gained from the metal complexes formed with the pyridyl ligand relative. The reported molecular structures with the pyridyl metal complexes all feature distorted octahedral geometry. In the case of (1), the thioether group sits above the neighbouring benzene ring, which would contribute to the formation of a distorted octahedral complex and remove the direct equatorial interaction of the sulfur to the donating nitrogen of the imine group. In addition, the pyrrole substituent is relatively less basic than pyridine, hence deprotonation of the pyrrole ligand must occur to elicit coordination of a metal centre.
All chemicals were purchased from commercial sources (Fisher Scientific and Sigma–Aldrich) and used without further purification. A colorless solution containing 0.683 g (7.18 mmol) of 2-pyrrolecarboxaldehyde dissolved in 15 mL of MeOH was added drop-wise to a light-green solution containing 1.00 g (7.18 mmol) of 2-(methylsulfanyl)aniline in 5 mL of MeOH with stirring. After refluxing the light-green solution overnight, the solution changed color to olive green. The solution was cooled to ambient temperature, and the solvent was removed under reduced pressure. The olive green residue was dissolved in 10 mL of MeOH, and was placed in the freezer at 263 K with a needle-punctured rubber septum. Crystals formed from the solution, and, after several days, were collected by vacuum filtration and washed with cold hexanes. 0.780 g (50%) of yellow crystals were isolated.
NMR spectra were recorded on a Bruker Avance II 400 MHz spectrometer operating at 400.17 MHz for 1H and 100.6 MHz for 13C, and were referenced to tetramethylsilane (δ = 0 p.p.m.). High-resolution MS data were obtained using a Waters XevoG2 QToF instrument in positive electrospray ionization mode. Theoretical m/z values are reported for an abundance greater than 10% of base signal. UV-Vis spectra were recorded in quartz cuvettes on a Varian Cary 100 Bio UV–Vis spectrometer. FT–IR spectra were recorded on a Thermo Nicolet 6700 FT–IR Spectrometer as KBr pellet (approximately 1.5 mg compound in 300 mg anhydrous KBr) in the 4,000 cm-1 to 400 cm-1 range with 2 cm-1 resolution.
Spectroscopic measurements confirmed the structure of (1). High-resolution π–π* transition of pyrrole and C═N bonds, respectively. The π–π* transition of benzene is also present with an absorbance around 350 nm.
gave an [M]+ ion of 217.0833 m/z, close to the calculated mass of 217.0755 m/z and the IR spectrum of (1) exhibited an imine stretch of 1611 cm-1 that is characteristic for aniline-based Absorbances located at 290 nm and 300 nm in the UV spectrum are characteristic of the1H NMR (400 MHz, CDCl3) δ = 9.63 (bs, 1H), 8.22 (s, 1H), 7.22–7.14 (m, 3H), 7.03 (bs, 1H), 6.99 (d, J = 7.6 Hz, 1H), 6.71 (dd, J = 1.2, 3.6 Hz, 1H), 6.34 (t, J = 2.8 Hz, 1H), 2.47 (s, 3H) p.p.m.13C{1H} NMR (100 MHz, CDCl3) δ = 149.1, 148.9, 133.9, 131.0, 125.9, 125.2, 124.3, 123.0, 117.5, 116.4, 110.6, 14.7 p.p.m. FT–IR (KBr) 3264, 3154, 2934, 3127, 3109. 3079, 3060, 2980, 2968, 2912, 2890, 2854, 1611, 1573, 1568, 1550, 1470, 1450, 1439, 1418, 1333, 1308, 1267, 1246, 1205, 1133, 1094, 1070, 1038, 975, 970, 956, 927, 882, 864, 844, 829, 781, 746, 725, 678, 603, 586 cm-1. HRMS (ESI–TOF) m/z: [M]+ Calculated for C12H12N2S 217.0755; found 217.0833. λmax/nm (DMF, 0.022 mg mL-1) 303 (λ/dm3 mol-1cm-1 21700), 270 (19100), 208 (sh).
Hydrogen atoms attached to carbons were assigned positions based on the sp2 or sp3
geometries of their attached atoms. Hydrogens attached to sp2-hybridized carbons were given isotropic displacement parameters 120% of those of the Ueq's for their attached atoms, while methyl-group hydrogens were given isotropic displacement parameters 150% of those for their attached carbons. The coordinates and displacement parameters for the hydrogens attached to N2 and O1S were allowed to refine freely.Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXD (Schneider & Sheldrick, 2002); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. Perspective view of the 2-methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline molecule showing the atom-labelling scheme. Non-hydrogen atoms are represented by Gaussian ellipsoids at the 30% probability level. | |
Fig. 2. Illustration of hydrogen-bonded interactions (dotted lines) between the2-methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline molecule and a nearby solvent methanol molecule. | |
Fig. 3. Packing view of (1) as viewed slightly offset from along the a axis. |
C12H12N2S·CH4O | F(000) = 528 |
Mr = 248.34 | Dx = 1.279 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5959 (4) Å | Cell parameters from 5994 reflections |
b = 7.0062 (4) Å | θ = 2.7–27.9° |
c = 24.4986 (14) Å | µ = 0.24 mm−1 |
β = 98.4543 (7)° | T = 193 K |
V = 1289.61 (12) Å3 | Fragment, colourless |
Z = 4 | 0.24 × 0.20 × 0.15 mm |
Bruker APEXII CCD diffractometer | 2579 reflections with I > 2σ(I) |
ω scans | Rint = 0.025 |
Absorption correction: integration (SADABS; Bruker, 2013) | θmax = 28.1°, θmin = 1.7° |
Tmin = 0.935, Tmax = 1.000 | h = −9→9 |
10802 measured reflections | k = −9→9 |
3055 independent reflections | l = −31→32 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.0414P)2 + 0.4071P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.090 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.28 e Å−3 |
3055 reflections | Δρmin = −0.20 e Å−3 |
165 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0044 (11) |
C12H12N2S·CH4O | V = 1289.61 (12) Å3 |
Mr = 248.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.5959 (4) Å | µ = 0.24 mm−1 |
b = 7.0062 (4) Å | T = 193 K |
c = 24.4986 (14) Å | 0.24 × 0.20 × 0.15 mm |
β = 98.4543 (7)° |
Bruker APEXII CCD diffractometer | 3055 independent reflections |
Absorption correction: integration (SADABS; Bruker, 2013) | 2579 reflections with I > 2σ(I) |
Tmin = 0.935, Tmax = 1.000 | Rint = 0.025 |
10802 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.28 e Å−3 |
3055 reflections | Δρmin = −0.20 e Å−3 |
165 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
S | 0.27868 (4) | 0.27649 (5) | 0.03023 (2) | 0.02884 (11) | |
N1 | 0.43422 (14) | 0.29520 (16) | 0.14334 (4) | 0.0274 (2) | |
N2 | 0.19082 (15) | 0.38459 (17) | 0.21958 (5) | 0.0308 (3) | |
H2N | 0.169 (2) | 0.457 (3) | 0.1897 (7) | 0.049 (5)* | |
C1 | 0.50824 (16) | 0.24857 (17) | 0.05218 (5) | 0.0242 (3) | |
C2 | 0.56495 (17) | 0.25724 (17) | 0.10935 (5) | 0.0255 (3) | |
C3 | 0.74554 (18) | 0.24302 (19) | 0.12952 (6) | 0.0309 (3) | |
H3 | 0.7846 | 0.2513 | 0.1681 | 0.037* | |
C4 | 0.86910 (17) | 0.2168 (2) | 0.09371 (6) | 0.0338 (3) | |
H4 | 0.9922 | 0.2080 | 0.1078 | 0.041* | |
C5 | 0.81268 (18) | 0.2034 (2) | 0.03767 (6) | 0.0340 (3) | |
H5 | 0.8972 | 0.1837 | 0.0132 | 0.041* | |
C6 | 0.63324 (17) | 0.21859 (19) | 0.01680 (6) | 0.0296 (3) | |
H6 | 0.5955 | 0.2085 | −0.0218 | 0.036* | |
C7 | 0.2639 (2) | 0.2898 (2) | −0.04355 (6) | 0.0345 (3) | |
H7A | 0.3419 | 0.3918 | −0.0533 | 0.052* | |
H7B | 0.1408 | 0.3171 | −0.0598 | 0.052* | |
H7C | 0.3011 | 0.1678 | −0.0578 | 0.052* | |
C8 | 0.44496 (18) | 0.21148 (19) | 0.19028 (5) | 0.0289 (3) | |
H8 | 0.5356 | 0.1188 | 0.1998 | 0.035* | |
C9 | 0.32524 (18) | 0.25263 (19) | 0.22884 (5) | 0.0280 (3) | |
C10 | 0.31947 (19) | 0.1746 (2) | 0.28029 (5) | 0.0330 (3) | |
H10 | 0.3969 | 0.0790 | 0.2977 | 0.040* | |
C11 | 0.1793 (2) | 0.2613 (2) | 0.30227 (6) | 0.0362 (3) | |
H11 | 0.1440 | 0.2356 | 0.3372 | 0.043* | |
C12 | 0.10244 (19) | 0.3905 (2) | 0.26377 (5) | 0.0348 (3) | |
H12 | 0.0039 | 0.4705 | 0.2675 | 0.042* | |
O1S | 0.15530 (14) | 0.62192 (16) | 0.12144 (4) | 0.0388 (3) | |
H1SO | 0.221 (3) | 0.551 (4) | 0.1064 (10) | 0.090 (8)* | |
C1S | 0.2439 (2) | 0.7991 (2) | 0.12954 (7) | 0.0493 (4) | |
H1SA | 0.2039 | 0.8659 | 0.1607 | 0.074* | |
H1SB | 0.2167 | 0.8768 | 0.0961 | 0.074* | |
H1SC | 0.3726 | 0.7775 | 0.1375 | 0.074* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S | 0.02473 (17) | 0.0349 (2) | 0.02682 (18) | −0.00058 (12) | 0.00369 (12) | −0.00038 (13) |
N1 | 0.0292 (5) | 0.0298 (6) | 0.0235 (5) | −0.0037 (4) | 0.0048 (4) | −0.0030 (4) |
N2 | 0.0348 (6) | 0.0332 (6) | 0.0238 (5) | 0.0001 (5) | 0.0020 (4) | 0.0037 (5) |
C1 | 0.0252 (6) | 0.0213 (6) | 0.0265 (6) | −0.0033 (4) | 0.0054 (5) | −0.0004 (5) |
C2 | 0.0274 (6) | 0.0223 (6) | 0.0274 (6) | −0.0025 (5) | 0.0055 (5) | −0.0006 (5) |
C3 | 0.0304 (6) | 0.0302 (7) | 0.0310 (7) | −0.0018 (5) | 0.0007 (5) | 0.0017 (5) |
C4 | 0.0236 (6) | 0.0322 (7) | 0.0452 (8) | −0.0007 (5) | 0.0035 (5) | −0.0003 (6) |
C5 | 0.0292 (6) | 0.0333 (8) | 0.0421 (8) | −0.0020 (5) | 0.0135 (6) | −0.0056 (6) |
C6 | 0.0304 (6) | 0.0305 (7) | 0.0294 (7) | −0.0040 (5) | 0.0089 (5) | −0.0042 (5) |
C7 | 0.0400 (7) | 0.0345 (8) | 0.0273 (7) | −0.0033 (6) | −0.0006 (5) | 0.0031 (5) |
C8 | 0.0309 (6) | 0.0283 (7) | 0.0274 (6) | −0.0039 (5) | 0.0043 (5) | −0.0017 (5) |
C9 | 0.0313 (6) | 0.0276 (7) | 0.0246 (6) | −0.0035 (5) | 0.0028 (5) | 0.0002 (5) |
C10 | 0.0367 (7) | 0.0346 (7) | 0.0271 (7) | −0.0008 (6) | 0.0029 (5) | 0.0058 (5) |
C11 | 0.0413 (8) | 0.0446 (8) | 0.0234 (6) | −0.0034 (6) | 0.0072 (5) | 0.0013 (6) |
C12 | 0.0346 (7) | 0.0392 (8) | 0.0312 (7) | 0.0007 (6) | 0.0068 (5) | −0.0027 (6) |
O1S | 0.0424 (6) | 0.0343 (6) | 0.0414 (6) | 0.0066 (5) | 0.0124 (5) | 0.0013 (5) |
C1S | 0.0525 (9) | 0.0449 (10) | 0.0524 (10) | −0.0038 (8) | 0.0144 (8) | −0.0030 (8) |
S—C1 | 1.7586 (13) | C7—H7A | 0.9800 |
S—C7 | 1.7968 (14) | C7—H7B | 0.9800 |
N1—C8 | 1.2829 (17) | C7—H7C | 0.9800 |
N1—C2 | 1.4118 (16) | C8—C9 | 1.4334 (18) |
N2—C12 | 1.3557 (17) | C8—H8 | 0.9500 |
N2—C9 | 1.3714 (17) | C9—C10 | 1.3806 (18) |
N2—H2N | 0.884 (18) | C10—C11 | 1.401 (2) |
C1—C6 | 1.3924 (17) | C10—H10 | 0.9500 |
C1—C2 | 1.4049 (18) | C11—C12 | 1.374 (2) |
C2—C3 | 1.3915 (18) | C11—H11 | 0.9500 |
C3—C4 | 1.388 (2) | C12—H12 | 0.9500 |
C3—H3 | 0.9500 | O1S—C1S | 1.412 (2) |
C4—C5 | 1.380 (2) | O1S—H1SO | 0.83 (3) |
C4—H4 | 0.9500 | C1S—H1SA | 0.9800 |
C5—C6 | 1.3878 (19) | C1S—H1SB | 0.9800 |
C5—H5 | 0.9500 | C1S—H1SC | 0.9800 |
C6—H6 | 0.9500 | ||
C1—S—C7 | 103.05 (7) | S—C7—H7C | 109.5 |
C8—N1—C2 | 119.01 (12) | H7A—C7—H7C | 109.5 |
C12—N2—C9 | 109.42 (11) | H7B—C7—H7C | 109.5 |
C12—N2—H2N | 126.0 (11) | N1—C8—C9 | 122.40 (13) |
C9—N2—H2N | 124.6 (11) | N1—C8—H8 | 118.8 |
C6—C1—C2 | 119.34 (12) | C9—C8—H8 | 118.8 |
C6—C1—S | 124.24 (10) | N2—C9—C10 | 107.17 (12) |
C2—C1—S | 116.42 (9) | N2—C9—C8 | 123.75 (12) |
C3—C2—C1 | 119.51 (12) | C10—C9—C8 | 129.07 (13) |
C3—C2—N1 | 123.11 (12) | C9—C10—C11 | 107.89 (13) |
C1—C2—N1 | 117.19 (11) | C9—C10—H10 | 126.1 |
C4—C3—C2 | 120.54 (13) | C11—C10—H10 | 126.1 |
C4—C3—H3 | 119.7 | C12—C11—C10 | 106.98 (12) |
C2—C3—H3 | 119.7 | C12—C11—H11 | 126.5 |
C5—C4—C3 | 119.86 (13) | C10—C11—H11 | 126.5 |
C5—C4—H4 | 120.1 | N2—C12—C11 | 108.53 (13) |
C3—C4—H4 | 120.1 | N2—C12—H12 | 125.7 |
C4—C5—C6 | 120.39 (13) | C11—C12—H12 | 125.7 |
C4—C5—H5 | 119.8 | C1S—O1S—H1SO | 106.4 (18) |
C6—C5—H5 | 119.8 | O1S—C1S—H1SA | 109.5 |
C5—C6—C1 | 120.32 (13) | O1S—C1S—H1SB | 109.5 |
C5—C6—H6 | 119.8 | H1SA—C1S—H1SB | 109.5 |
C1—C6—H6 | 119.8 | O1S—C1S—H1SC | 109.5 |
S—C7—H7A | 109.5 | H1SA—C1S—H1SC | 109.5 |
S—C7—H7B | 109.5 | H1SB—C1S—H1SC | 109.5 |
H7A—C7—H7B | 109.5 | ||
C7—S—C1—C6 | −7.76 (13) | C2—C1—C6—C5 | −2.00 (19) |
C7—S—C1—C2 | 172.43 (10) | S—C1—C6—C5 | 178.18 (10) |
C6—C1—C2—C3 | 2.43 (18) | C2—N1—C8—C9 | 175.38 (11) |
S—C1—C2—C3 | −177.75 (10) | C12—N2—C9—C10 | 0.08 (15) |
C6—C1—C2—N1 | 177.62 (11) | C12—N2—C9—C8 | −179.73 (13) |
S—C1—C2—N1 | −2.55 (15) | N1—C8—C9—N2 | −0.6 (2) |
C8—N1—C2—C3 | −41.88 (18) | N1—C8—C9—C10 | 179.65 (14) |
C8—N1—C2—C1 | 143.11 (12) | N2—C9—C10—C11 | −0.04 (16) |
C1—C2—C3—C4 | −1.2 (2) | C8—C9—C10—C11 | 179.75 (13) |
N1—C2—C3—C4 | −176.13 (12) | C9—C10—C11—C12 | −0.01 (16) |
C2—C3—C4—C5 | −0.4 (2) | C9—N2—C12—C11 | −0.08 (16) |
C3—C4—C5—C6 | 0.9 (2) | C10—C11—C12—N2 | 0.06 (17) |
C4—C5—C6—C1 | 0.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1S | 0.884 (18) | 2.025 (18) | 2.9030 (16) | 172.0 (16) |
O1S—H1SO···S | 0.83 (3) | 2.76 (3) | 3.5134 (12) | 152 (2) |
O1S—H1SO···N1 | 0.83 (3) | 2.49 (2) | 3.1116 (16) | 132 (2) |
C7—H7B···O1Si | 0.98 | 2.55 | 3.5181 (18) | 168 |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1S | 0.884 (18) | 2.025 (18) | 2.9030 (16) | 172.0 (16) |
O1S—H1SO···S | 0.83 (3) | 2.76 (3) | 3.5134 (12) | 152 (2) |
O1S—H1SO···N1 | 0.83 (3) | 2.49 (2) | 3.1116 (16) | 132 (2) |
C7—H7B···O1Si | 0.98 | 2.55 | 3.5181 (18) | 167.9 |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C12H12N2S·CH4O |
Mr | 248.34 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 193 |
a, b, c (Å) | 7.5959 (4), 7.0062 (4), 24.4986 (14) |
β (°) | 98.4543 (7) |
V (Å3) | 1289.61 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.24 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Integration (SADABS; Bruker, 2013) |
Tmin, Tmax | 0.935, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10802, 3055, 2579 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.663 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.090, 1.04 |
No. of reflections | 3055 |
No. of parameters | 165 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.20 |
Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXD (Schneider & Sheldrick, 2002), SHELXL2014 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors thank NSERC and Cape Breton University for financial support of this research. We also thank M. C. Larade for assistance with data file compilation.
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