Synthesis, mol­ecular structure and Hirshfeld surface analysis of (4-meth­oxy­phen­yl)[2-(methyl­sulfan­yl)thio­phen-3-yl]methanone

The title mol­ecule is substanti­ally twisted, with a dihedral angle of 43.70 (2)° between the 2-(methyl­sulfan­yl)thio­phene and 4-meth­oxy­phenyl rings. In the crystal, mol­ecules are linked through C—H⋯O inter­actions, forming a bifurcated layer stacking along the b-axis direction enclosing (10) ring motifs.

Abstract

The title compound, C₁₃H₁₂O₂S₂, crystallizes in the triclinic space group P . The mol­ecular structure is substanti­ally twisted, with a dihedral angle of 43.70 (2)° between the 2-(methyl­sulfan­yl)thio­phene and 4-meth­oxy­phenyl rings. In the crystal, mol­ecules are linked through C—H⋯O inter­actions and form a bifurcated layer stacking along the b-axis direction and enclosing R ₂ ²(10) ring motifs. The phenyl rings are involved in π–π inter­actions with a centroid–centroid separation of 3.760 (2) Å. The Hirshfeld surfaces were studied and the contributions of the various inter­molecular inter­actions were qu­anti­fied.

Chemical context  

Thio­phenes are five-membered sulfur-containing heterocyclic compounds with important applications in areas such as agrochemistry, pharmaceuticals, mol­ecular electronics, liquid crystalline materials and corrosion inhibition. Thio­phenes are also important building blocks in organic synthesis. Their aromatic character gives enough stabilization to allow the manipulation of various substituents (Mishra et al., 2011 ▸). α-Oxoketene thio­acetals are powerful building blocks for the synthesis of numerous heterocyclic scaffolds, where the carbonyl carbon generally provides hard centers and the carbon-bearing methyl­sulfanyl group acts as a soft electrophilic center (Junjappa et al., 1990 ▸). This synthetic building block was used for the synthesis of (4-meth­oxy­phen­yl) [2-(methyl­sulfan­yl)thio­phen-3-yl]methanone (Pradeepa Kumara et al., 2016 ▸).

Structural commentary  

In the title compound, the 2-(methyl­sulfan­yl)thio­phene and 4-meth­oxy­phenyl aromatic rings are connected via a C(=O)—C methanone bridge (Fig. 1 ▸). The compound is substanti­ally twisted about the methanone bridge as indicated by the dihedral angle of 43.70 (2)° between the thio­phene (S1/C1/C5/C7/C10) and phenyl (C2–C6/C11/C13) rings. The methyl group at S2 is in a +syn-periplanar conformation, as indicated by the C8—S2—C10—S1 torsion angle of 6.09 (16)°. However, in the related compound (4-fluoro­phen­yl)[2-(methyl­sulfan­yl)thio­phen-3-yl]methanone (Nagaraju et al., 2018 ▸), this group is in a -syn-periplanar conformation with a torsion angle of −1.7 (2)°. Atom C12 adopts a nearly trigonal geometry, as indicated by the bond angles C7–C12–O2 = 119.5 (2)°, O2–C12–C4 = 119.2 (2)° and C4—C12—C7 = 121.3 (2)°. The meth­oxy group attached at C11 is in a −anti-periplanar conformation [C3—C11—O1—C9 = −176.9 (2)°]. The bond lengths and angles are normal (Sreenatha et al., 2017 ▸; Rajni Swamy et al., 2014 ▸; Gopinath et al., 2016 ▸).

Figure 1.

Mol­ecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level.

Supra­molecular features  

The crystal structure features inter­molecular hydrogen-bonding inter­actions of the type C9—H9A⋯O2 (Fig. 2 ▸, Table 1 ▸) and displays a bifurcated layer stacking along the b-axis direction through C6—H6⋯O2 inter­actions, which link inversion-related mol­ecules into dimers enclosing an (10) ring motif. π–π stacking inter­actions are also observed between the phenyl rings (centroid Cg) of adjacent mol­ecules [Cg⋯ Cg(2 − x, −y, 1 − z) = 3.760 (2) Å]. The packing of the title compound is illustrated in Fig. 3 ▸.

Figure 2.

The (10) ring motif formed via inter­molecular C6—H6⋯O2 hydrogen bonds (Table 1 ▸). The π–π inter­actions are also shown.

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2i	0.93	2.48	3.374 (4)	161
C9—H9A⋯O2ii	0.96	2.45	3.400 (4)	172

Symmetry codes: (i) ; (ii) .

Figure 3.

Packing for of the title compound viewed along the b axis.

Hirshfeld surfaces and 2D fingerprint plots  

Hirshfeld surface (HS) analysis and the associated fingerprint plots (FP) (CrystalExplorer; Spackman & Jayatilaka, 2009 ▸) are useful tools for visualizing the types of inter­molecular inter­actions present in a crystal structure and qu­antify their percentage contributions to the crystal packing. The 3D HS mapped over d _norm between −0.2106 a.u (blue) and 1.2279 a.u (red) is shown in Fig. 4 ▸. The area and volume of the HS are 287.29 Ų and 305.24 ų, respectively. The deep-red spots on the d _norm surface are due to the presence of inter­molecular C—H⋯O inter­actions (Sreenatha et al., 2018 ▸). The 2D FP analysis (Fig. 5 ▸) shows that the H⋯H contacts make the highest contribution (39.3%) followed by the H⋯C/C⋯H contacts (20.1%), which are seen as a pair of blunt spikes in the region 1.2 Å < (d _i + d _e) < 1.75 Å. The H⋯S/S⋯H contacts make a contribution of 16.9% and appear as butterfly wings in the region 1.2 Å < (d _i + d _e) < 1.9 Å. The pair of sharp spikes is observed in the region 1.2 Å < (d _i + d _e) < 1.32 Å is due to the presence of H⋯O/O⋯H contacts (15.6% contribution). The C⋯C contacts (3.4% contribution) are visible as wings in almost the same region, 1.7 Å < (d _i + d _e) < 1.72 Å. The relative contributions of all the contacts to the Hirshfeld surface are depicted in Fig. 6 ▸.

Figure 4.

Hirshfeld surface for the title compound mapped over d _norm in the range −0.2106 to 1.2279 a.u. highlighting the C—H⋯O inter­molecular inter­actions.

Figure 5.

The full two-dimensional fingerprint plots for the title compound, showing (a) all inter­actions, and delineated into (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯S/S⋯H, (e) H⋯O/O⋯H, (f) C⋯C, (g) S⋯C/C⋯S and (h) S⋯S inter­actions. The d _i and d _e values are the closest inter­nal and external distances (in Å) from given points on the Hirshfeld surface.

Figure 6.

The relative contributions (%) to the Hirshfeld surface for the various contacts.

Database survey  

A search for thio­phene derivatives was carried out in the Cambridge Structural Database (CSD, Version 5.39, update of February 2018; Groom et al., 2016 ▸). The most relevant compounds are 5-[bis­(4-eth­oxy­phen­yl)amino]­thio­phene-2-carbaldehyde (HOJCIU; Tan et al., 2014 ▸) and 2-[4-(benz­yloxy)phen­yl]-5-(3,4-di­meth­oxy­phen­yl)-3, 4-di­methyl­thio­phene (ACETEI; Shi et al., 2004 ▸), which are both non-planar. In ethyl 4-acetyl-5-anilino-3-methyl­thio­phene-2-carboxyl­ate (AFIGIH; Mabkhot et al., 2013 ▸), the thio­phene and phenyl rings make a dihedral angle of 36.81 (10)°.

Synthesis and crystallization  

To α-oxoketene di­thio­acetal (0.1 mol) and 1,4-di­thiane-2,5-diol (0.05 mol) in dry ethanol (10 mL), anhydrous potassium carbonate (0.12 mol) was added. The reaction mixture was refluxed on a water bath for 30 minutes (the condenser being protected by a calcium chloride guard tube). After completion of the reaction (monitored by TLC), the catalyst was filtered off and washed with fresh ethanol. The combined ethanol solution was removed on a rotary evaporator to obtain a viscous liquid. The crude product was purified by column chromatography using silica gel with 5% ethyl acetate and petroleum ether to yield the title compound as a yellow solid product, which was recrystallized from di­chloro­methane solution. M.p. 489–493 K. IR (KBr) ν_max = 3449, 3079, 2923, 2841, 1772, 1600, 1493, 1253, 1167, 1015, 842, 694, 550 cm⁻¹. ¹H NMR (300 MHz, CDCl₃): 7.79–7.77 (m, 2 H), 7.27–7.25 (m, 1H), 7.16–7.14 (m, 1H), 6.9–6.93 (m, 2H), 3.86 (s, 3H), 2.58 (s, 3H) ppm. ¹³ C NMR (75 MHz, CDCl₃): 188.86, 162.73, 151.33, 135.36, 131.60, 131.47, 130.24, 130.59, 122.02, 113.44, 55.37, 18.06. HRMS (ESI): calculated for C₁₃H₁₂O₂S₂ [M + H]⁺ 265.0312; found 265.0407.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All hydrogen atoms were placed at calculated positions and refined using a riding model with C—H = 0.93 Å and U _iso(H) = 1.2U _eq(C) for aromatic ring atoms and with C—H = 0.96 Å with U _iso(H) = 1.5U _eq(C) for methyl groups.

Table 2. Experimental details.

Crystal data
Chemical formula	C13H12O2S2
M r	264.35
Crystal system, space group	Triclinic, P
Temperature (K)	293
a, b, c (Å)	7.806 (4), 8.263 (3), 10.414 (6)
α, β, γ (°)	97.260 (11), 109.65 (2), 93.79 (2)
V (Å3)	623.3 (5)
Z	2
Radiation type	Mo Kα
μ (mm−1)	0.41
Crystal size (mm)	0.30 × 0.26 × 0.20
Data collection
Diffractometer	Bruker APEX
No. of measured, independent and observed [I > 2σ(I)] reflections	2924, 2165, 1899
R int	0.109
(sin θ/λ)max (Å−1)	0.595
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.046, 0.128, 1.09
No. of reflections	2165
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.37, −0.33

Computer programs: APEX2 (Bruker, 2006 ▸), SAINT (Bruker, 2006 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2018 (Sheldrick, 2015 ▸), PLATON (Spek, 2009 ▸) and Mercury (Macrae et al., 2008 ▸), PLATON (Spek, 2009 ▸).

Supplementary Material

CCDC reference: 1871776

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

C13H12O2S2	Z = 2
Mr = 264.35	F(000) = 276
Triclinic, P1	Dx = 1.409 Mg m−3
a = 7.806 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.263 (3) Å	Cell parameters from 2924 reflections
c = 10.414 (6) Å	θ = 3.5–25.0°
α = 97.260 (11)°	µ = 0.41 mm−1
β = 109.65 (2)°	T = 293 K
γ = 93.79 (2)°	Block, colourless
V = 623.3 (5) Å3	0.30 × 0.26 × 0.20 mm

Data collection

Bruker APEX diffractometer	1899 reflections with I > 2σ(I)
Radiation source: graphite	Rint = 0.109
Detector resolution: 0.894 pixels mm-1	θmax = 25.0°, θmin = 3.5°
SAINT (Bruker, 2006) [not correct; type of scans needed]	h = −9→9
2924 measured reflections	k = −9→9
2165 independent reflections	l = −12→11

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.046	w = 1/[σ2(Fo2) + (0.072P)2 + 0.1135P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.128	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 0.37 e Å−3
2165 reflections	Δρmin = −0.33 e Å−3
157 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.060 (18)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.77364 (8)	0.32143 (7)	−0.09953 (6)	0.0412 (3)
S2	0.73606 (8)	0.60555 (7)	0.10012 (6)	0.0422 (3)
O1	0.7606 (3)	−0.1498 (2)	0.62854 (18)	0.0582 (5)
O2	0.7950 (3)	0.4642 (2)	0.33504 (18)	0.0601 (5)
C1	0.8084 (3)	0.1302 (3)	−0.0527 (3)	0.0450 (6)
H1	0.820956	0.039871	−0.110524	0.054*
C2	0.6715 (3)	0.0359 (3)	0.3139 (2)	0.0419 (6)
H2	0.607492	0.011357	0.219380	0.050*
C3	0.8621 (3)	0.1072 (3)	0.5930 (2)	0.0437 (6)
H3	0.927331	0.131023	0.687398	0.052*
C4	0.7766 (3)	0.1880 (3)	0.3679 (2)	0.0361 (5)
C5	0.8153 (3)	0.1275 (3)	0.0773 (2)	0.0402 (5)
H5	0.834586	0.034541	0.119774	0.048*
C6	0.8701 (3)	0.2215 (3)	0.5107 (2)	0.0407 (5)
H6	0.938609	0.323029	0.550038	0.049*
C7	0.7900 (3)	0.2813 (3)	0.1446 (2)	0.0352 (5)
C8	0.6913 (4)	0.6721 (3)	−0.0642 (3)	0.0525 (6)
H8A	0.594501	0.598579	−0.133310	0.079*
H8B	0.800026	0.672480	−0.087893	0.079*
H8C	0.655487	0.781032	−0.059371	0.079*
C9	0.6614 (5)	−0.3123 (4)	0.5746 (3)	0.0726 (9)
H9A	0.704580	−0.365458	0.505805	0.109*
H9B	0.533040	−0.303439	0.533903	0.109*
H9C	0.681017	−0.375822	0.648323	0.109*
C10	0.7680 (3)	0.4010 (3)	0.0595 (2)	0.0341 (5)
C11	0.7571 (3)	−0.0450 (3)	0.5371 (2)	0.0426 (5)
C12	0.7881 (3)	0.3201 (3)	0.2846 (2)	0.0397 (5)
C13	0.6597 (3)	−0.0792 (3)	0.3964 (2)	0.0459 (6)
H13	0.586967	−0.179094	0.358019	0.055*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0427 (4)	0.0471 (4)	0.0361 (4)	0.0025 (3)	0.0176 (3)	0.0050 (3)
S2	0.0402 (4)	0.0346 (4)	0.0488 (4)	−0.0026 (2)	0.0148 (3)	0.0010 (2)
O1	0.0729 (13)	0.0652 (12)	0.0423 (10)	0.0013 (10)	0.0272 (9)	0.0124 (8)
O2	0.0870 (15)	0.0460 (10)	0.0429 (10)	0.0040 (9)	0.0214 (9)	−0.0041 (8)
C1	0.0512 (14)	0.0421 (13)	0.0453 (13)	0.0072 (10)	0.0235 (11)	0.0008 (10)
C2	0.0356 (12)	0.0535 (14)	0.0302 (10)	−0.0047 (10)	0.0073 (9)	−0.0002 (9)
C3	0.0400 (12)	0.0615 (15)	0.0258 (10)	0.0005 (11)	0.0106 (9)	−0.0013 (10)
C4	0.0325 (11)	0.0448 (12)	0.0296 (10)	−0.0001 (9)	0.0115 (8)	0.0009 (9)
C5	0.0409 (12)	0.0393 (12)	0.0421 (12)	0.0079 (9)	0.0157 (10)	0.0067 (9)
C6	0.0375 (12)	0.0484 (13)	0.0311 (11)	−0.0036 (10)	0.0110 (9)	−0.0048 (9)
C7	0.0290 (10)	0.0398 (11)	0.0335 (11)	0.0008 (8)	0.0089 (8)	0.0007 (9)
C8	0.0504 (15)	0.0444 (13)	0.0623 (16)	−0.0009 (11)	0.0170 (12)	0.0173 (12)
C9	0.108 (3)	0.0627 (18)	0.0627 (18)	−0.0042 (17)	0.0516 (18)	0.0122 (14)
C10	0.0243 (10)	0.0389 (11)	0.0356 (11)	−0.0033 (8)	0.0096 (8)	−0.0005 (9)
C11	0.0407 (13)	0.0548 (14)	0.0372 (11)	0.0036 (11)	0.0204 (9)	0.0068 (10)
C12	0.0351 (12)	0.0443 (12)	0.0336 (11)	−0.0001 (9)	0.0080 (9)	−0.0026 (9)
C13	0.0409 (13)	0.0528 (14)	0.0387 (12)	−0.0097 (11)	0.0129 (10)	−0.0014 (10)

Geometric parameters (Å, º)

S1—C10	1.719 (2)	C4—C6	1.400 (3)
S1—C1	1.724 (3)	C4—C12	1.494 (3)
S2—C10	1.744 (2)	C5—C7	1.430 (3)
S2—C8	1.793 (3)	C5—H5	0.9300
O1—C11	1.360 (3)	C6—H6	0.9300
O1—C9	1.448 (4)	C7—C10	1.391 (3)
O2—C12	1.230 (3)	C7—C12	1.458 (3)
C1—C5	1.340 (4)	C8—H8A	0.9600
C1—H1	0.9300	C8—H8B	0.9600
C2—C13	1.379 (3)	C8—H8C	0.9600
C2—C4	1.394 (3)	C9—H9A	0.9600
C2—H2	0.9300	C9—H9B	0.9600
C3—C6	1.365 (3)	C9—H9C	0.9600
C3—C11	1.397 (4)	C11—C13	1.387 (3)
C3—H3	0.9300	C13—H13	0.9300
C10—S1—C1	92.19 (11)	S2—C8—H8A	109.5
C10—S2—C8	100.76 (12)	S2—C8—H8B	109.5
C11—O1—C9	117.8 (2)	H8A—C8—H8B	109.5
C5—C1—S1	111.72 (18)	S2—C8—H8C	109.5
C5—C1—H1	124.1	H8A—C8—H8C	109.5
S1—C1—H1	124.1	H8B—C8—H8C	109.5
C13—C2—C4	121.9 (2)	O1—C9—H9A	109.5
C13—C2—H2	119.0	O1—C9—H9B	109.5
C4—C2—H2	119.0	H9A—C9—H9B	109.5
C6—C3—C11	120.7 (2)	O1—C9—H9C	109.5
C6—C3—H3	119.6	H9A—C9—H9C	109.5
C11—C3—H3	119.6	H9B—C9—H9C	109.5
C2—C4—C6	117.6 (2)	C7—C10—S1	110.79 (16)
C2—C4—C12	124.3 (2)	C7—C10—S2	127.08 (17)
C6—C4—C12	118.1 (2)	S1—C10—S2	122.13 (14)
C1—C5—C7	113.6 (2)	O1—C11—C13	125.0 (2)
C1—C5—H5	123.2	O1—C11—C3	115.7 (2)
C7—C5—H5	123.2	C13—C11—C3	119.3 (2)
C3—C6—C4	121.0 (2)	O2—C12—C7	119.5 (2)
C3—C6—H6	119.5	O2—C12—C4	119.2 (2)
C4—C6—H6	119.5	C7—C12—C4	121.33 (19)
C10—C7—C5	111.7 (2)	C2—C13—C11	119.5 (2)
C10—C7—C12	120.6 (2)	C2—C13—H13	120.3
C5—C7—C12	127.7 (2)	C11—C13—H13	120.3
C10—S1—C1—C5	0.0 (2)	C8—S2—C10—S1	6.09 (16)
C13—C2—C4—C6	−0.5 (4)	C9—O1—C11—C13	2.7 (4)
C13—C2—C4—C12	−177.3 (2)	C9—O1—C11—C3	−176.9 (2)
S1—C1—C5—C7	0.8 (3)	C6—C3—C11—O1	179.4 (2)
C11—C3—C6—C4	−1.4 (4)	C6—C3—C11—C13	−0.2 (4)
C2—C4—C6—C3	1.7 (3)	C10—C7—C12—O2	−11.1 (3)
C12—C4—C6—C3	178.7 (2)	C5—C7—C12—O2	168.1 (2)
C1—C5—C7—C10	−1.4 (3)	C10—C7—C12—C4	168.49 (19)
C1—C5—C7—C12	179.4 (2)	C5—C7—C12—C4	−12.4 (4)
C5—C7—C10—S1	1.3 (2)	C2—C4—C12—O2	141.9 (3)
C12—C7—C10—S1	−179.42 (16)	C6—C4—C12—O2	−34.8 (3)
C5—C7—C10—S2	−179.26 (16)	C2—C4—C12—C7	−37.6 (3)
C12—C7—C10—S2	0.0 (3)	C6—C4—C12—C7	145.6 (2)
C1—S1—C10—C7	−0.78 (18)	C4—C2—C13—C11	−1.1 (4)
C1—S1—C10—S2	179.77 (14)	O1—C11—C13—C2	−178.2 (2)
C8—S2—C10—C7	−173.3 (2)	C3—C11—C13—C2	1.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2i	0.93	2.48	3.374 (4)	161
C9—H9A···O2ii	0.96	2.45	3.400 (4)	172

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y−1, z.