Structure and spectroscopic properties of N,S-coordinating 2-methyl­sulfanyl-N-[(1H-pyrrol-2-yl)methyl­idene]aniline methanol monosolvate

Richards, D.D.; Ang, M.T.C.; McDonald, R.; Bierenstiel, M.

doi:10.1107/S205698901501590X

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages 1136-1139

doi:10.1107/S205698901501590X

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Structure and spectroscopic properties of N,S-coordinating 2-methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline methanol monosolvate

D. Douglas Richards,^a ^* M. Trisha C. Ang,^a Robert McDonald ^a,^b and Matthias Bierenstiel ^a

^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

Edited by R. F. Baggio, Comisión Nacional de Energía Atómica, Argentina (Received 12 August 2015; accepted 25 August 2015; online 12 September 2015)

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⋯O_methanol 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.

Figure 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.

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].

Table 1
Hydrogen-bond geometry (Å, °)

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.

Figure 2
Illustration of hydrogen-bonded interactions (dotted lines) between the 2-methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline molecule and a nearby solvent methanol molecule.

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⋯O_methanol interactions, forming inversion dimers consisting of two main molecules and two solvent molecules (Table 1).

Figure 3
Packing view of (1) as viewed slightly offset from along the a axis.

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 chelation, 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 space group P $[\overline{1}]$ . 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 mass spectrometry 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 imines. 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. λ_max/nm (DMF, 0.022 mg mL⁻¹) 303 (λ/dm³ mol⁻¹cm⁻¹ 21700), 270 (19100), 208 (sh).

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms attached to carbons were assigned positions based on the sp² or sp³ hybridization geometries of their attached atoms. Hydrogens attached to sp²-hybridized carbons were given isotropic displacement parameters U_iso(H) = 1.2U_iso(C) for their attached atoms, while methyl-group hydrogens were given isotropic displacement parameters U_iso(H) = 1.5U_eq(C) for their attached carbons. The coordinates and displacement parameters for the hydrogens attached to N2 and O1S were allowed to refine freely.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂S·CH₄O
M_r	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
Absorption correction	Integration (SADABS; Bruker, 2013 )
T_min, T_max	0.935, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10802, 3055, 2579
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.20
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXD (Schneider & Sheldrick, 2002 ), SHELXL2014 (Sheldrick, 2015 ), SHELXTL (Sheldrick, 2008 ) and Mercury (Macrae et al., 2006 ).

Supporting information

CCDC reference: 1417853

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S205698901501590X/bg2566sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S205698901501590X/bg2566Isup2.hkl

Supporting information file. DOI: 10.1107/S205698901501590X/bg2566Isup3.cml

checkCIF report

Chemical context top

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.

Structural commentary top

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].

Supramolecular features top

Table 1 provides information on hydrogen-bonding interactions and Fig. 3 illustrates the crystal packing as viewed roughly along the a axis of the unit cell. 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. Weak intermolecular C—H···X interactions are observed: C7—H7B···O1S(-x, 1 - y, -z) = 2.55 Å.

Thioether bonding in related structures top

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 space group 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.

Synthesis and crystallization top

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.

Spectroscopic investigations top

Spectroscopic measurements confirmed the structure of (1). High-resolution mass spectrometry 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 imines. 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. λ_max/nm (DMF, 0.022 mg mL^-1) 303 (λ/dm³ mol^-1cm^-1 21700), 270 (19100), 208 (sh).

Refinement details top

Hydrogen atoms attached to carbons were assigned positions based on the sp² or sp³ hybridization geometries of their attached atoms. Hydrogens attached to sp²-hybridized carbons were given isotropic displacement parameters 120% of those of the U_eq'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.

Related literature top

For related literature, see: Addison et al. (1984); Alberto Acosta-Ramirez, Larade, Lloy, Cross, McLellan, Martell, McDonald & Bierenstiel (2013); Basuli et al. (1996); Chou et al. (2008); Cross et al. (2011, 2014); Ham et al. (2006); He et al. (2009); Schnödt et al. (2011); Klinman (2006); McIntyre et al. (2009); Jana et al. (2013); Mu et al. (2011); Balamurugan et al. (2006); Parveen et al. (2005); Patra et al. (2011a, 2011b) Chatterjee et al. 2012); Muthiah et al. (2014, 2015); Schwindt et al. (1976a, 1976b); Setifi et al. (2014).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: 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).

Figures top

	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.

2-Methylsulfanyl-N-[(1H-pyrrol-2-yl)methylidene]aniline methanol monosolvate top

Crystal data top

C₁₂H₁₂N₂S·CH₄O	F(000) = 528
M_r = 248.34	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	2579 reflections with I > 2σ(I)
ω scans	R_int = 0.025
Absorption correction: integration (SADABS; Bruker, 2013)	θ_max = 28.1°, θ_min = 1.7°
T_min = 0.935, T_max = 1.000	h = −9→9
10802 measured reflections	k = −9→9
3055 independent reflections	l = −31→32

Refinement top

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(F_o²) + (0.0414P)² + 0.4071P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.090	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.28 e Å⁻³
3055 reflections	Δρ_min = −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)

Crystal data top

C₁₂H₁₂N₂S·CH₄O	V = 1289.61 (12) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	3055 independent reflections
Absorption correction: integration (SADABS; Bruker, 2013)	2579 reflections with I > 2σ(I)
T_min = 0.935, T_max = 1.000	R_int = 0.025
10802 measured reflections

Refinement top

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	Δρ_max = 0.28 e Å⁻³
3055 reflections	Δρ_min = −0.20 e Å⁻³
165 parameters

Special details top

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

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.935, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10802, 3055, 2579
R_int	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
Δρ_max, Δρ_min (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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